KR102004562B1 - Use of comb or block copolymers as soil antiredeposition agents and soil release agents in laundry processes - Google Patents
Use of comb or block copolymers as soil antiredeposition agents and soil release agents in laundry processes Download PDFInfo
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- KR102004562B1 KR102004562B1 KR1020147013605A KR20147013605A KR102004562B1 KR 102004562 B1 KR102004562 B1 KR 102004562B1 KR 1020147013605 A KR1020147013605 A KR 1020147013605A KR 20147013605 A KR20147013605 A KR 20147013605A KR 102004562 B1 KR102004562 B1 KR 102004562B1
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- comb
- block copolymer
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- 238000000034 method Methods 0.000 title claims abstract description 19
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- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
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- 150000002976 peresters Chemical class 0.000 description 1
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- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IWELDVXSEVIIGI-UHFFFAOYSA-N piperazin-2-one Chemical class O=C1CNCCN1 IWELDVXSEVIIGI-UHFFFAOYSA-N 0.000 description 1
- CNMSOWSDPDRHAM-UHFFFAOYSA-N piperazine-2-thione Chemical compound S=C1CNCCN1 CNMSOWSDPDRHAM-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 235000018102 proteins Nutrition 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- GHKCMSLSUYMTNI-UHFFFAOYSA-M sodium;3-benzoyloxy-4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1OC(=O)C1=CC=CC=C1 GHKCMSLSUYMTNI-UHFFFAOYSA-M 0.000 description 1
- XVESOXRSUKAXRD-UHFFFAOYSA-M sodium;3-benzoyloxy-4-methylbenzoate Chemical compound [Na+].CC1=CC=C(C([O-])=O)C=C1OC(=O)C1=CC=CC=C1 XVESOXRSUKAXRD-UHFFFAOYSA-M 0.000 description 1
- OVONNAXAHAIEDF-UHFFFAOYSA-M sodium;4-benzoyloxybenzenesulfonate Chemical compound [Na+].C1=CC(S(=O)(=O)[O-])=CC=C1OC(=O)C1=CC=CC=C1 OVONNAXAHAIEDF-UHFFFAOYSA-M 0.000 description 1
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- 239000000375 suspending agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- KHJNXCATZZIGAX-UHFFFAOYSA-N tert-butyl 2-ethyl-2-methylheptaneperoxoate Chemical compound CCCCCC(C)(CC)C(=O)OOC(C)(C)C KHJNXCATZZIGAX-UHFFFAOYSA-N 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
본 발명은 세탁 과정에서의 오염 재부착방지제 및 방오제로서의 제어 자유 라디칼 중합에 의해 제조된 빗살형 또는 블록 공중합체의 용도에 관한 것이다. 본 발명의 추가 측면은 세탁 과정에서 오염 재부착을 방지하고 텍스타일로부터 오염을 보다 용이하게 방출시키는 방법, 및 상기 빗살형 또는 블록 공중합체를 함유하는 세제 제제이다.The present invention relates to an anti-fouling agent and a use of a comb or block copolymer produced by controlled free radical polymerization as an antifouling agent in a washing process. A further aspect of the present invention is a method of preventing contamination adherence during washing and more easily releasing contamination from textile, and a detergent formulation containing said comb or block copolymer.
Description
본 발명은 세탁 과정에서의 오염 재부착방지제 및 방오제로서의 제어 자유 라디칼 중합에 의해 제조된 빗살형 또는 블록 공중합체의 용도에 관한 것이다. 본 발명의 추가 측면은 세탁 과정에서 오염 재부착을 방지하고 텍스타일로부터 오염을 보다 용이하게 방출시키는 방법, 및 상기 빗살형 또는 블록 공중합체를 함유하는 세제 제제이다.The present invention relates to an anti-fouling agent and a use of a comb or block copolymer produced by controlled free radical polymerization as an antifouling agent in a washing process. A further aspect of the present invention is a method of preventing contamination adherence during washing and more easily releasing contamination from textile, and a detergent formulation containing said comb or block copolymer.
통상의 가정 세척 방법에서, 오염은, 특히 차선의 세제 제제를 사용하는 경우에 및/또는 보다 낮은 세척 온도에서, 더러운 텍스타일로부터 세척액으로 방출된 후에 다시 텍스타일에 재부착될 수 있다. 이러한 경우에, 다중-사이클 세척 후에 세탁물의 회색화가 나타나게 된다. 추가의 문제점은 차선의 세제 제제를 사용하는 경우에 및/또는 보다 낮은 세척 온도에서 텍스타일로부터 일부 유형의 오염 및 오물을 제거하기 어렵다는 점이며, 이는 이러한 오염 및 오물이 섬유 표면에 강하게 붙어 있거나 섬유 내에 강하게 흡수되어 있기 때문이다.In conventional home cleaning methods, contamination can be redeposited back to the textile, especially after the liquor detergent formulation is used and / or at lower wash temperatures, after being released from the dirty textile into the wash liquor. In this case, the graying of the laundry appears after multi-cycle cleaning. A further problem is that it is difficult to remove some types of contamination and dirt from the textile when using a second-hand detergent formulation and / or at a lower cleaning temperature, since this contamination and dirt are strongly stuck to the fiber surface, It is strongly absorbed.
세탁 과정에서의 오염 재부착방지제 및 방오제로서의 여러 작용제의 용도는 공지되어 있다. 예는 카르복시메틸 셀룰로스 또는 테레프탈산 및 폴리에틸렌 글리콜로부터의 중합체의 음이온성 유도체이다 (예를 들어, 문헌 [E. Smulders in "Laundry Detergents" Wiley-VCH Verlag GmbH, 2002, page 88] 참조). 오염 재부착방지제는 다양한 메카니즘에 의해 작용할 수 있다. 방오제에 관하여, 이들은 세탁물 세척 동안 섬유 표면 상에 부착 및 축적되어서, 섬유의 표면 특성을 변형시키는 것으로 종종 추정된다. 이러한 변형된 섬유 표면 상에 후속적으로 부착되는 오염 및 오물은 후속 세척 사이클에서 보다 용이하게 방출된다.The use of various agents as antifouling agents and antifouling agents in washing processes is well known. Examples are carboxymethylcellulose or anionic derivatives of polymers from terephthalic acid and polyethylene glycols (e. G., E. Smulders in "Laundry Detergents" Wiley-VCH Verlag GmbH, 2002, page 88). The anti-fouling agent can act by various mechanisms. With respect to antifouling agents, they are often assumed to adhere and accumulate on the fiber surface during laundry washing, thereby altering the surface properties of the fiber. The contaminants and dirt which subsequently adhere to these deformed fiber surfaces are more easily released in subsequent washing cycles.
본 발명의 목적은, 세탁 과정에서 오염 재부착을 방지할 수 있고 텍스타일로부터 오염 및 오물을 보다 용이하게 방출시킬 수 있게 하는, 가정 분야에 적합한 개선된 방법을 제공하는 것이다. 추가의 목적은 그 방법에 적합한 세척 제제를 제공하는 것이다.It is an object of the present invention to provide an improved method suitable for the household sector which makes it possible to prevent contamination adherence during the washing process and to more easily release pollution and dirt from the textile. A further object is to provide a cleaning formulation suitable for the method.
놀랍게도, 언급된 목적은 제어 자유 라디칼 중합에 의해 제조된 다음에 중합체 유사 에스테르교환 처리된 빗살형 또는 블록 공중합체의 사용에 의해 대부분 충족될 수 있는 것으로 밝혀졌다.Surprisingly, it has been found that the stated objectives can be largely met by the use of controlled free radical polymerization followed by the use of polymer-like transesterified comb or block copolymers.
본 발명의 한 측면은 수성 세탁 과정에서의 오염 재부착방지제 및 방오제로서의 1종 이상의 빗살형 또는 블록 공중합체의 용도로서, 상기 빗살형 또는 블록 공중합체는 제1 단계에서One aspect of the present invention is the use of at least one comb or block copolymer as an antifouling agent and an antifouling agent in an aqueous washing process,
a) 아크릴산 또는 메타크릴산의 C1-C10 알킬 에스테르 및 임의로 1종 이상의 에스테르 결합 무함유 단량체의 제어 자유 라디칼 중합에 의해 제조되고; 제2 단계에서a) prepared by controlled free radical polymerization of a C 1 -C 10 alkyl ester of acrylic acid or methacrylic acid and optionally at least one ester-free bond-free monomer; In the second step
b) 1급 또는 2급 알콜을 사용한 중합체 유사 에스테르교환 반응으로 개질되어b) modified by polymeric transesterification using primary or secondary alcohols
빗살형 또는 블록 공중합체가 형성된다.Comb-shaped or block copolymer is formed.
제어 자유 라디칼 중합 (controlled free radical polymerisation; CFRP)은 세척 과정 동안 그들을 오염 재부착방지제 또는 방오제로서 사용하기 위한 도구인 것으로 밝혀졌다. CFRP와 안정화 블록의 후속적 후-개질과의 조합은 상기 언급된 세제 용도로 사용될 수 있는 가능한 군을 확장시킨다. 하나의 CFRP-공정을 사용하여 많은 다양한 중합체 물질들이 이용 가능해진다. 이러한 2 단계 반응으로 제조된 빗살형 및 블록 공중합체는 예를 들어 WO 2006/0074969에 기재되어 있다.Controlled free radical polymerization (c ontrolled r adical f ree p olymerisation; CFRP) have been found to be a tool to use them in pollution reattachment inhibitor or as an antifouling agent for the cleaning process. The combination of CFRP and subsequent post-reforming of the stabilization block expands the possible families that can be used for the above-mentioned detergent applications. Many different polymeric materials become available using a single CFRP-process. Comb and block copolymers prepared by this two step reaction are described, for example, in WO 2006/0074969.
알콕시아민 또는 안정한 니트록실 라디칼을 사용하는 제어 자유 라디칼 중합은 널리 공지된 기술이며, 지난 20년 동안 광범위하게 기재되었다.Controlled free radical polymerization using alkoxy amines or stable nitroxyl radicals is a well known technique and has been extensively described over the past two decades.
예를 들어 US 4,581,429에는 중합체 쇄의 성장을 제어하여 단쇄 또는 올리고머 단독중합체 및 공중합체를 제조하는 자유 라디칼 중합 방법이 개시되어 있다. 상기 방법은 화학식 (일부) R'R"N-O-X를 갖는 개시제를 이용하며, 여기서 X는 불포화 단량체들을 중합시킬 수 있는 자유 라디칼 종이고, 라디칼 
US 5,322,912에는 니트록실 라디칼에 의해 종결된 단독중합체 및 블록 공중합체의 합성을 위해 자유 라디칼 개시제, 중합성 단량체 화합물 및 기본 구조 
보다 최근에 추가의 니트록실 라디칼 및 니트록실 에테르가 기재되었다. WO 98/13392에는 예를 들어 대칭적 치환 패턴을 갖고 NO 기체로부터 또는 니트로소 화합물로부터 유도되는 개방 쇄 알콕시아민 화합물이 기재되어 있다.More recently, additional nitroxyl radicals and nitrosyl ethers have been described. WO 98/13392 discloses open chain alkoxyamine compounds having, for example, symmetrical substitution patterns and derived from NO gas or from nitroso compounds.
WO 96/24620에는 예를 들어 
WO 98/30601에는 이미다졸리딘온 기재의 특정한 니트록실이 개시되어 있다.WO 98/30601 discloses certain nitroxyls based on imidazolidinones.
WO 98/44008에는 모르폴리논, 피페라지논 및 피페라진디온 기재의 특정한 니트록실이 개시되어 있다.WO 98/44008 discloses certain nitroxyls based on morpholinones, piperazinones and piperazinethione.
이들 선행 기술의 니트록실 라디칼 및 니트록실 에테르는 모두 본 발명에 적합하다.Both of these prior art nitroxyl radicals and nitrosyl ethers are suitable for the present invention.
본 발명에 적합한 니트록실에테르 및 니트록실 라디칼은 주로 US 4,581,429 또는 EP-A-621 878에 공지되어 있다. WO 98/13392, WO 99/03894 및 WO 00/07981에 기재된 개방 쇄 화합물, WO 99/67298, GB 2335190 및 GB 2 361 235에 기재된 피페리딘 유도체, 또는 GB 2342649 및 WO 96/24620에 기재된 헤테로시클릭 화합물이 특히 유용하다. 최근에 추가의 니트록실 라디칼 및 니트록실 에테르가 WO 02/48205, WO02/48109 및 WO 02/100831에 기재되었다.Nitroxyl ether and nitroxyl radicals suitable for the present invention are known in the art, primarily from US 4,581,429 or EP-A-621 878. The open chain compounds described in WO 98/13392, WO 99/03894 and WO 00/07981, the piperidine derivatives described in WO 99/67298, GB 2335190 and GB 2 361 235, or the heterocyclic derivatives described in GB 2342649 and WO 96/24620 Cyclic compounds are particularly useful. More recently, nitroxyl radicals and nitrosyl ethers have been described in WO 02/48205, WO 02/48109 and WO 02/100831.
문헌 [Chem. Commun., 2001, 823-824]에 기재된 화합물이 또한 적합하다.Chem. Commun., 2001, 823-824 are also suitable.
일부 화합물은 상업적으로 입수가능하거나, 상기 언급된 문헌에 따라 제조될 수 있다.Some compounds are commercially available or may be prepared according to the above-mentioned references.
예를 들어, 알콕시아민, 
<화학식 I>(I)
<화학식 II>≪
상기 식에서,In this formula,
G1, G2, G3, G4는 독립적으로 C1-C6알킬이거나, 또는 G1 및 G2 또는 G3 및 G4, 또는 G1 및 G2 및 G3 및 G4는 함께 C5-C12시클로알킬 기를 형성하고;G 1, G 2, G 3, G 4 are independently C 1 -C 6 alkyl or, or G 1 and G 2 or G 3 and G 4, or G 1 and G 2 and G 3 and G 4 together are C 5 form a group -C 12 cycloalkyl;
G5, G6은 독립적으로 H, C1-C18알킬, 페닐, 나프틸 또는 기 COOC1-C18알킬이고;G 5 , and G 6 are independently H, C 1 -C 18 alkyl, phenyl, naphthyl or a group COOC 1 -C 18 alkyl;
X는 -CH2-페닐, CH3CH-페닐, (CH3)2C-페닐, (C5-C6시클로알킬)2CCN, (CH3)2CCN, 
*는 원자가를 나타낸다.* Represents a valence.
매우 구체적인 실시양태에서 제어 자유 라디칼 중합에 사용되는 알콕시아민은 하기 화학식 NOR01의 화합물이다.In a very specific embodiment, the alkoxyamine used in the controlled free radical polymerization is a compound of the formula < RTI ID = 0.0 > NOR01 < / RTI >
<화학식 NOR01><Formula NOR01>
알콕시아민 화합물은 바람직하게는 단량체를 기준으로 하여 0.01 mol% 내지 30 mol%의 양, 보다 바람직하게는 0.1 mol% 내지 20 mol%의 양, 가장 바람직하게는 0.1 mol% 내지 10 mol%의 양으로 사용된다.The alkoxyamine compound is preferably present in an amount of from 0.01 mol% to 30 mol%, more preferably from 0.1 mol% to 20 mol%, most preferably from 0.1 mol% to 10 mol%, based on the monomers Is used.
CFRP는 "리빙" 중합이기 때문에, 이는 사실상 마음대로 출발 및 중지될 수 있다. 또한, 중합체 생성물은 중합을 리빙 방식으로 지속시키는 관능성 알콕시아민 기를 보유한다. 따라서, 일단 제1 단량체가 초기 중합 단계에서 소모되면, 이어서 제2 단량체가 첨가되어 제2 중합 단계에서 성장하는 중합체 쇄 상에 제2 블록이 형성될 수 있다. 이에 따라, 동일 또는 상이한 단량체(들)을 사용하는 첨가 중합을 수행하여 다중-블록 공중합체를 제조하는 것이 가능하다.Since CFRP is a "living" polymerization, this can in fact be started and stopped at will. In addition, the polymer product possesses a functional alkoxyamine group that persists the polymerization in a living manner. Thus, once the first monomer is consumed in the initial polymerization step, then a second monomer may be added to form a second block on the polymer chain growing in the second polymerization step. Thus, it is possible to carry out addition polymerization using the same or different monomer (s) to produce multi-block copolymers.
또한, 이는 라디칼 중합이기 때문에, 블록은 본질적으로 임의의 순서로 제조될 수 있다. 블록 공중합체의 제조는, 이온 중합에서의 경우와 같이 순차적 중합 단계가 가장 덜 안정한 중합체 중간체로부터 가장 많이 안정한 중합체 중간체로 진행되어야 하는 것으로 반드시 제한되는 것은 아니다. 따라서, 폴리아크릴로니트릴 또는 폴리(메트)아크릴레이트 블록을 먼저 제조한 다음, 이에 스티렌 블록을 부착시켜 다중-블록 공중합체를 제조하는 것이 가능하다.Also, since it is a radical polymerization, the blocks can be prepared in essentially any order. The preparation of block copolymers is not necessarily limited to the sequential polymerization step as in the case of ionic polymerization, from the least stable polymer intermediate to the most stable polymer intermediate. Accordingly, it is possible to prepare a polyacrylonitrile or poly (meth) acrylate block first, and then attach a styrene block thereto to prepare a multi-block copolymer.
또한, 본 블록 공중합체의 다양한 블록을 연결하기 위해 연결기가 필요한 것은 아니다. 간단하게, 연속적으로 단량체들을 첨가하여 연속적인 블록을 형성할 수 있다. 블록은 이전 및 이후 블록 둘 다의 단량체들이 상이한 비율로 존재하는 테이퍼링된 구역에 의해 분리될 수도 있다.Also, a linking group is not required to link various blocks of the present block copolymer. Briefly, successive monomers can be added to form a continuous block. The block may be separated by a tapered zone in which the monomers of both the previous and subsequent blocks are present in different ratios.
다수의 특별히 고안된 중합체 및 공중합체는 예를 들어 특히 문헌 [C. J. Hawker in Angew. Chemie, 1995, 107, pages 1623-1627]에 기재된 바와 같은 별형 및 그라프트 (공)중합체, 문헌 [K. Matyaszewski et al. in Macromolecules 1996, Vol 29, No. 12, pages 4167-4171]에 기재된 바와 같은 덴드리머, 문헌 [C. J. Hawker et al. in Macromol. Chem. Phys. 198, 155-166(1997)]에 기재된 바와 같은 그라프트 (공)중합체, 문헌 [C. J. Hawker in Macromolecules 1996, 29, 2686-2688]에 기재된 바와 같은 랜덤 공중합체, 또는 문헌 [N. A. Listigovers in Macromolecules 1996, 29, 8992-8993]에 기재된 이블록 또는 삼블록 공중합체에 의해 입수가능하다.Many specially designed polymers and copolymers are described, for example, in < RTI ID = 0.0 > C. < / RTI > J. Hawker in Angew. Chemie, 1995, 107, pages 1623-1627, K. K. et al. Matyaszewski et al. in Macromolecules 1996, Vol. 12, pages 4167-4171], dendrimers as described in [C. J. Hawker et al. in Macromol. Chem. Phys. 198, 155-166 (1997)); graft (co) polymers such as those described in [C.I. J. Hawker in Macromolecules 1996, 29, 2686-2688; or a random copolymer as described in N. A. Listigovers in Macromolecules 1996, 29, 8992-8993.
예를 들어, 빗살형 또는 블록 공중합체는 1.0 내지 2.5, 바람직하게는 1.1 내지 2.0의 다분산도, PD를 갖는다.For example, the comb or block copolymer has a polydispersity, PD, of 1.0 to 2.5, preferably 1.1 to 2.0.
바람직한 실시양태에서 빗살형 또는 블록 공중합체는 친양쪽성 특성을 갖는다.In a preferred embodiment, the comb or block copolymer has pro-amorphous properties.
바람직하게는 빗살형 또는 블록 공중합체는 단계 a)에서 n-부틸아크릴레이트 및 임의로 1종 이상의 에스테르 결합 무함유 단량체로부터 제조된다.Preferably the comb or block copolymer is prepared from n-butyl acrylate and optionally one or more ester bond-free monomers in step a).
예를 들어, 에스테르 결합 무함유 단량체는 4-비닐-피리딘, 2-비닐-피리딘, 비닐-이미다졸, 비닐-피롤리돈, 디메틸아크릴아미드, 3-디메틸아미노프로필메타크릴아미드, 스티렌, α-메틸 스티렌, p-메틸 스티렌 또는 p-tert-부틸-스티렌, 아크릴로니트릴로 이루어진 군으로부터 선택된다. 아민성 단량체는 또한 그의 이온화된 또는 4급화된 형태로 사용될 수 있거나, 또는 연속적 단계에서 추후 개질될 수 있다.For example, the ester bond-free monomers can be selected from the group consisting of 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, vinyl-pyrrolidone, dimethyl acrylamide, 3-dimethylaminopropyl methacrylamide, Methyl styrene, p-methyl styrene or p-tert-butyl styrene, acrylonitrile. Amine-containing monomers may also be used in their ionized or quaternized form, or may be subsequently modified in subsequent steps.
제어 자유 라디칼 중합을 니트록실 라디칼을 사용하여 수행하는 경우에, 개시하는 라디칼 공급원이 추가로 필요하다. 이러한 라디칼 공급원 개시제는 바람직하게는 아조 화합물, 퍼옥시드, 퍼에스테르 또는 히드로퍼옥시드이다.When controlled free radical polymerization is carried out using nitroxyl radicals, there is a further need for a starting radical source. Such radical source initiators are preferably azo compounds, peroxides, peresters or hydroperoxides.
특정한 바람직한 라디칼 공급원은 2,2'-아조비스이소부티로니트릴, 2,2'-아조비스(2-메틸부티로니트릴), 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 1,1'-아조비스(1-시클로헥산카르보니트릴), 2,2'-아조비스(이소부티르아미드) 2수화물, 2-페닐아조-2,4-디메틸-4-메톡시발레로니트릴, 디메틸-2,2'-아조비스이소부티레이트, 2-(카르바모일아조)이소부티로니트릴, 2,2'-아조비스(2,4,4-트리메틸펜탄), 2,2'-아조비스(2-메틸프로판), 2,2'-아조비스(N,N'-디메틸렌이소부티르아미딘), 유리 염기 또는 히드로클로라이드, 2,2'-아조비스(2-아미디노프로판), 유리 염기 또는 히드로클로라이드, 2,2'-아조비스{2-메틸-N-[1,1-비스(히드록시메틸)에틸]프로피온아미드} 또는 2,2'-아조비스{2-메틸-N-[1,1-비스(히드록시메틸)-2-히드록시에틸]프로피온아미드; 아세틸 시클로헥산 술포닐 퍼옥시드, 디이소프로필 퍼옥시 디카르보네이트, t-아밀 퍼네오데카노에이트, t-부틸 퍼네오데카노에이트, t-부틸 퍼피발레이트, t-아밀퍼피발레이트, 비스(2,4-디클로로벤조일)퍼옥시드, 디이소노나노일 퍼옥시드, 디데카노일 퍼옥시드, 디옥타노일 퍼옥시드, 디라우로일 퍼옥시드, 비스 (2-메틸벤조일) 퍼옥시드, 디숙신산 퍼옥시드, 디아세틸 퍼옥시드, 디벤조일 퍼옥시드, t-부틸 퍼 2-에틸헥사노에이트, 비스-(4-클로로벤조일)-퍼옥시드, t-부틸 퍼이소부티레이트, t-부틸 퍼말레이네이트, 1,1-비스(t-부틸퍼옥시)3,5,5-트리메틸시클로헥산, 1,1-비스(t-부틸퍼옥시)시클로헥산, t-부틸 퍼옥시 이소프로필 카르보네이트, t-부틸 퍼이소노나오에이트, 2,5-디메틸헥산 2,5-디벤조에이트, t-부틸 퍼아세테이트, t-아밀 퍼벤조에이트, t-부틸 퍼벤조에이트, 2,2-비스 (t-부틸퍼옥시) 부탄, 2,2 비스 (t-부틸퍼옥시) 프로판, 디쿠밀 퍼옥시드, 2,5-디메틸헥산-2,5-디-t-부틸퍼옥시드, 3-t-부틸퍼옥시 3-페닐프탈리드, 디-t-아밀 퍼옥시드, α,α'-비스(t-부틸퍼옥시 이소프로필) 벤젠, 3,5-비스 (t-부틸퍼옥시)3,5-디메틸 1,2-디옥솔란, 디-t-부틸 퍼옥시드, 2,5-디메틸헥신-2,5-디-t-부틸퍼옥시드, 3,3,6,6,9,9-헥사메틸 1,2,4,5-테트라옥사 시클로노난, p-멘탄 히드로퍼옥시드, 피난 히드로퍼옥시드, 디이소프로필벤젠 모노-α-히드로퍼옥시드, 쿠멘 히드로퍼옥시드 또는 t-부틸 히드로퍼옥시드이다.Particularly preferred radical sources are 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) , 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile) Amide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2'-azobisisobutyrate, 2- (carbamoyl azo) isobutyronitrile, 2 , 2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (N, N'-dimethyleneisobutyramine ), Free base or hydrochloride, 2,2'-azobis (2-amidinopropane), free base or hydrochloride, 2,2'-azobis {2-methyl-N- [ (Hydroxymethyl) -2-hydroxypropyl] propionamide) or 2,2'-azobis {2-methyl-N- [ Mead; Amyl perene decanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amyl perpivalate, bis (2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauryl peroxide, bis (2-methylbenzoyl) peroxide, (4-chlorobenzoyl) -peroxide, t-butylperisobutyrate, t-butylpermalate, t-butylperoxylate, t-butylperoxylate, Butylperoxy) cyclohexane, t-butylperoxyisopropylcarbonate, t-butyl (t-butylperoxy) 2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl peroxide (T-butylperoxy) propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t- Butyl peroxide, 3-t-butylperoxy-3-phenylphthalide, di-t-amyl peroxide,?,? '- bis (t- butylperoxyisopropyl) Butyl peroxy) 3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexine-2,5-di-t-butyl peroxide, , 9,9-hexamethyl 1,2,4,5-tetraoxacyclononane, p-menthihydroperoxide, pinanhydroperoxide, diisopropylbenzene mono -? - hydroperoxide, cumene hydroperoxide or t -Butyl hydroperoxide.
라디칼 공급원은 단량체를 기준으로 하여 바람직하게는 0.01 mol% 내지 30 mol%의 양, 보다 바람직하게는 0.1 mol% 내지 20 mol%의 양, 가장 바람직하게는 0.5 mol% 내지 10 mol%의 양으로 존재한다.The radical source is preferably present in an amount of from 0.01 mol% to 30 mol%, more preferably from 0.1 mol% to 20 mol%, most preferably from 0.5 mol% to 10 mol%, based on the monomers do.
라디칼 공급원 대 니트록실 라디칼의 몰비는 1:10 내지 10:1, 바람직하게는 1:5 내지 5:1, 보다 바람직하게는 1:2 내지 2:1일 수 있다.The molar ratio of the radical source to the nitrosyloxy radical may be from 1:10 to 10: 1, preferably from 1: 5 to 5: 1, more preferably from 1: 2 to 2: 1.
CFRP 단계 a)를 위한 반응 조건은 상기 열거된 문헌에 광범위하게 기재되어 있다. 일반적으로 중합 온도는 정상 압력에서 60 내지 180℃이며, 반응 시간은 30분 내지 20시간으로 다양할 수 있다.The reaction conditions for CFRP step a) are extensively described in the above listed documents. Generally, the polymerization temperature is from 60 to 180 ° C at normal pressure, and the reaction time may vary from 30 minutes to 20 hours.
예를 들어 단계 b)의 에스테르교환에서의 1급 또는 2급 알콜은 하기 화학식 A의 에톡실레이트;For example, the primary or secondary alcohol in the ester exchange of step b) is an ethoxylate of formula A;
<화학식 A>≪ Formula (A)
(상기 식에서, RA는 1-22개의 탄소 원자를 갖는 포화 또는 불포화, 선형 또는 분지형 쇄 알킬, 또는 24개 이하의 탄소 원자를 갖는 알킬아릴 또는 디알킬아릴이고; n은 1 내지 150임)Wherein R A is a saturated or unsaturated, linear or branched chain alkyl having 1-22 carbon atoms, or alkylaryl or dialkylaryl having 24 or fewer carbon atoms; n is 1-150,
하기 화학식 B의 폴리디메틸실리콘 올리고머;A polydimethylsilicon oligomer of Formula B;
<화학식 B>≪ Formula B >
(상기 식에서, RB는 C1-C18알킬, 페닐 또는 C7-C15아르알킬이고; n은 1 내지 50이고; R'은 1 내지 20개의 탄소 원자를 갖는 연결기임)Wherein R B is C 1 -C 18 alkyl, phenyl or C 7 -C 15 aralkyl, n is 1 to 50, and R 'is a linking group having 1 to 20 carbon atoms,
부분 또는 완전 플루오린화 1급 알콜;Partially or fully fluorinated primary alcohols;
C8 내지 C60알킬 선형 또는 분지형 1급 또는 2급 알콜;C 8 to C 60 alkyl, linear or branched primary or secondary alcohols;
2,2-디메틸-4-히드록시메틸-1,3-디옥솔란의 라세미 혼합물;Racemic mixture of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane;
1개 이상의 3급 아민 기를 함유하는 1급 또는 2급 알콜, 예컨대 N,N,N'-트리메틸아미노에틸에탄올아민, 4-히드록시에틸-피리딘 및 N-히드록시에틸모르폴린; 또는Primary or secondary alcohols containing one or more tertiary amine groups such as N, N, N'-trimethylaminoethylethanolamine, 4-hydroxyethyl-pyridine and N-hydroxyethylmorpholine; or
쇄에 1개 이상의 에스테르 기가 개재된 1급 알콜, 예컨대 750 내지 2500 g/mol의 분자량을 갖는 폴리카프로락톤 α-세틸옥시,-ω-히드록시이다.Primary alcohols in which at least one ester group is interposed in the chain, such as polycaprolactone? -Cetyloxy,? -Hydroxy having a molecular weight of 750 to 2500 g / mol.
용어 알킬아릴에서, 아릴은 페닐 또는 나프틸을 의미하고, 알킬은 바람직하게는 C1-C20 선형 또는 분지형 알킬이다.In the term alkylaryl, aryl means phenyl or naphthyl, and alkyl is preferably C 1 -C 20 linear or branched alkyl.
구체적 실시양태에서 알콜은 부분 또는 완전 플루오린화 1급 알콜이다. 상업적으로 입수가능한 플루오린화 알콜 혼합물의 예는 다음과 같다: 듀폰(Du Pont)으로부터의 조닐(Zonyl) BA®, 조닐 BA-L®, 조닐 BA-LD®, 조닐 BA-N®, 옴노바 솔루션즈 인크(Omnova Solutions Inc)로부터의 플루오린화 폴리옥세탄 알콜.In a specific embodiment, the alcohol is a partial or complete fluorinated primary alcohol. Examples of commercially available fluorinated alcohol mixtures are as follows: Zonyl BA® from Du Pont, Zonyl BA-L®, Zonyl BA-LD®, Zonyl BA-N®, Fluorinated polyoxetane alcohols from Omnova Solutions Inc.
바람직하게는 단계 b)의 1급 알콜은 하기 화학식 A의 에톡실레이트;Preferably, the primary alcohol of step b) is an ethoxylate of formula A;
<화학식 A>≪ Formula (A)
(상기 식에서, RA는 1-22개의 탄소 원자를 갖는 포화 또는 불포화, 선형 또는 분지형 쇄 알킬이고; n은 1 내지 150임)Wherein R A is a saturated or unsaturated, linear or branched chain alkyl having 1 to 22 carbon atoms and n is 1 to 150,
2,2-디메틸-4-히드록시메틸-1,3-디옥솔란의 라세미 혼합물;Racemic mixture of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane;
N,N,N'-트리메틸아미노에틸에탄올아민;N, N, N'-trimethylaminoethylethanolamine;
N-히드록시에틸모르폴린; 또는N-hydroxyethylmorpholine; or
750 내지 2500 g/mol의 분자량을 갖는 폴리카프로락톤 α-세틸옥시,-ω-히드록시이다.-Caprolactone a-cetyloxy, -O-hydroxy having a molecular weight of 750 to 2500 g / mol.
전형적으로 수성 세탁 과정은 가정 세탁 과정이다.Typically, the aqueous wash process is a home laundry process.
예를 들어 텍스타일은 폴리에스테르, 폴리아크릴, 면, 울, 폴리아미드 또는 그의 혼합물로부터 제조되며, 바람직하게는 텍스타일은 면이다.For example, the textile is made from polyester, polyacryl, cotton, wool, polyamide or a mixture thereof, preferably the textile is cotton.
본 발명의 또 다른 측면은 빗살형 또는 블록 공중합체를 적용하는 것을 포함하는, 수성 세탁 과정 동안 텍스타일 상의 오염 재부착을 방지하고 텍스타일로부터 오염을 방출시키는 방법으로서, 상기 빗살형 또는 블록 공중합체는 제1 단계에서 Another aspect of the present invention is a method of preventing contamination of textile on the textile and releasing contamination from the textile during an aqueous laundering process, comprising applying a comb or block copolymer, wherein the comb or block copolymer comprises In Step 1
a) 아크릴산 또는 메타크릴산의 C1-C10 알킬 에스테르 및 임의로 1종 이상의 에스테르 결합 무함유 단량체의 제어 자유 라디칼 중합에 의해 제조되고; 제2 단계에서a) prepared by controlled free radical polymerization of a C 1 -C 10 alkyl ester of acrylic acid or methacrylic acid and optionally at least one ester-free bond-free monomer; In the second step
b) 1급 또는 2급 알콜을 사용한 중합체 유사 에스테르교환 반응으로 개질되어b) modified by polymeric transesterification using primary or secondary alcohols
빗살형 또는 블록 공중합체가 형성된다.Comb-shaped or block copolymer is formed.
빗살형 또는 블록 공중합체가 세제의 일부로서 사용되는 경우에, 이는 전체 세제 조성물의 중량을 기준으로 하여 0.05 내지 20 중량%의 양으로 존재할 수 있다.When a comb or block copolymer is used as part of a detergent, it may be present in an amount of from 0.05 to 20% by weight, based on the weight of the overall detergent composition.
본 발명의 추가 측면은 다음을 포함하는 세제 조성물이다:A further aspect of the present invention is a detergent composition comprising:
I) 조성물의 총 중량을 기준으로 하여 1 내지 50 중량%의 A) 1종 이상의 계면활성제;I) from 1 to 50% by weight, based on the total weight of the composition, A) at least one surfactant;
II) 조성물의 총 중량을 기준으로 하여 0 내지 70 중량%의 B) 1종 이상의 빌더 물질;II) from 0 to 70% by weight, based on the total weight of the composition, of B) one or more builder materials;
III) 조성물의 총 중량을 기준으로 하여 0 내지 30 중량%의 C) 1종 이상의 퍼옥시드 및/또는 퍼옥시드-형성 물질;III) from 0 to 30% by weight, based on the total weight of the composition, of C) at least one peroxide and / or peroxide-forming material;
IV) 조성물의 총 중량을 기준으로 하여 0.05 내지 10 중량%, 바람직하게는 0.05 내지 5 중량%, 보다 바람직하게는 0.1 내지 4 중량%의 D) 상기 정의된 바와 같은 1종 이상의 빗살형 또는 블록 공중합체;(D) 0.05 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, based on the total weight of the composition IV) coalescence;
V) 조성물의 총 중량을 기준으로 하여 0 내지 60 중량%의 E) 1종 이상의 추가의 첨가제; 및V) 0 to 60% by weight, based on the total weight of the composition E) at least one further additive; And
VI) 조성물의 총 중량을 기준으로 하여 0 내지 90 중량%의 F) 물.VI) from 0 to 90% by weight, based on the total weight of the composition, of F) water.
본 발명에 따른 조성물은, 예를 들어 고체 퍼옥시드-함유 중질 세제, 정밀 텍스타일을 위한 세제 분말, 유색 상품을 위한 세탁 세제 분말, 또는 구조화 (즉, 혼탁) 또는 비구조화 (즉, 투명) 수계 액체 세제일 수 있다.The compositions according to the present invention may be used in the form of, for example, solid peroxide-containing heavy detergents, detergent powders for fine textiles, laundry detergent powders for colored goods, or structured (i.e. turbid) or unstructured It may be a detergent.
성분 A)의 계면활성제The surfactant of component A)
세제 제제는 통상적으로 음이온성, 양이온성, 비이온성 또는 양쪽성일 수 있는 1종 이상의 계면활성제를 포함할 것이다.Detergent formulations will typically comprise one or more surfactants which may be anionic, cationic, nonionic or amphoteric.
음이온성 계면활성제는, 예를 들어 술페이트, 술포네이트 또는 카르복실레이트 계면활성제 또는 그의 혼합물일 수 있다. 바람직한 것은 알킬벤젠술포네이트, 알킬 술페이트, 알킬 에테르 술페이트, 올레핀 술포네이트, 지방산 염, 알킬 및 알케닐 에테르 카르복실레이트, 또는 α-술폰산 지방산 염 또는 그의 에스테르이다.The anionic surfactant can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preferred are alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates, or? -Sulfonic acid fatty acid salts or esters thereof.
바람직한 술포네이트는, 예를 들어 알킬 라디칼 내에 10 내지 20개의 탄소 원자를 갖는 알킬벤젠술포네이트, 알킬 라디칼 내에 8 내지 18개의 탄소 원자를 갖는 알킬 술페이트, 알킬 라디칼 내에 8 내지 18개의 탄소 원자를 갖는 알킬 에테르 술페이트, 및 팜 오일 또는 탈로우로부터 유도되고 알킬 모이어티 내에 8 내지 18개의 탄소 원자를 갖는 지방산 염이다. 알킬 에테르 술페이트에 부가된 에틸렌 옥시드 단위의 평균 몰 수는 1 내지 20이고, 바람직하게는 1 내지 10이다. 음이온성 계면활성제의 양이온은 바람직하게는 알칼리 금속 양이온, 특히 나트륨 또는 칼륨, 보다 특히 나트륨이다. 바람직한 카르복실레이트는 화학식 R19'-CON(R20')CH2COOM1의 알칼리 금속 사르코시네이트이며, 여기서 R19'은 C9-C17알킬 또는 C9-C17알케닐이고, R20'은 C1-C4알킬이고, M1은 알칼리 금속, 특히 나트륨이다.Preferred sulfonates are, for example, alkylbenzene sulfonates having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical, alkyl radicals having from 8 to 18 carbon atoms in the alkyl radical Alkyl ether sulfates, and fatty acid salts derived from palm oil or tallow and having 8 to 18 carbon atoms in the alkyl moiety. The average number of moles of ethylene oxide units added to the alkyl ether sulfates is 1 to 20, preferably 1 to 10. The cation of the anionic surfactant is preferably an alkali metal cation, especially sodium or potassium, more particularly sodium. Preferred carboxylates are alkali metal sarcosinates of the formula R 19 ' -CON (R 20' ) CH 2 COOM 1 wherein R 19 ' is C 9 -C 17 alkyl or C 9 -C 17 alkenyl, R 20 ' is C 1 -C 4 alkyl and M 1 is an alkali metal, especially sodium.
비이온성 계면활성제는, 예를 들어 1급 또는 2급 알콜 에톡실레이트, 특히 알콜 기당 평균 1 내지 20 mol의 에틸렌 옥시드로 에톡실화된 C8-C20 지방족 알콜일 수 있다. 바람직한 것은 알콜 기당 평균 1 내지 10 mol의 에틸렌 옥시드로 에톡실화된 1급 및 2급 C10-C15 지방족 알콜이다. 비-에톡실화 비이온성 계면활성제, 예를 들어 알킬폴리글리코시드, 글리세롤 모노에테르 및 폴리히드록시아미드 (글루카미드)도 마찬가지로 사용될 수 있다.A non-ionic surfactant may be, for example, rate, especially alcohol gidang average 1 to 20 mol of ethylene oxide draw ethoxylated C 8 -C 20 aliphatic alcohols ethoxylated primary or secondary alcohol. Preference is given to ethylene dioxydroethoxylated primary and secondary C 10 -C 15 aliphatic alcohols on average from 1 to 10 mol per alcohol group. Non-ethoxylated nonionic surfactants such as alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamides) may also be used.
음이온성 및/또는 비이온성 계면활성제 이외에, 조성물은 양이온성 계면활성제를 함유할 수 있다. 가능한 양이온성 계면활성제는 모든 통상의 양이온성 표면-활성 화합물, 특히 텍스타일 유연화 효과를 갖는 계면활성제를 포함한다.In addition to the anionic and / or nonionic surfactants, the compositions may contain cationic surfactants. Possible cationic surfactants include all conventional cationic surface-active compounds, especially those having a textile softening effect.
양이온성 계면활성제의 비제한적 예는 하기 화학식으로 나타내어진다:Non-limiting examples of cationic surfactants are represented by the formula:
상기 식들에서,In the above equations,
각각의 라디칼 Rα는 서로 독립적으로 C1 -6-알킬-, -알케닐- 또는 -히드록시알킬이고; 각각의 라디칼 Rβ는 서로 독립적으로 C8 -28-알킬- 또는 알케닐이고;Each of the radicals R α is independently from each other C 1 -6-alkyl -, - alkenyl-or-hydroxy-alkyl; Each radical R β are independently C 8 -28 each other alkyl- or alkenyl;
Rγ는 Rα 또는 (CH2)n-T-Rβ이고;R γ R α is or (CH 2) n -TR β and;
Rδ는 Rα 또는 Rβ 또는 (CH2)n-T-Rβ이고; T = -CH2-, -O-CO- 또는 -CO-O-이고;R is R δ α or β, or R (CH 2) n -TR β and; T = -CH 2 -, -O- CO- or -CO-O-, and;
n은 0 내지 5이다.n is 0-5.
본 발명에 따른 조성물 중에 존재하는 바람직한 양이온성 계면활성제는 히드록시알킬-트리알킬-암모늄-화합물, 특히 C12 - 18알킬(히드록시에틸)디메틸암모늄 화합물, 특히 바람직하게는 상응하는 클로라이드 염을 포함한다.Preferred cationic surface active agent present in the composition according to the present invention is a hydroxy-alkyl-trialkyl-ammonium-compounds, in particular C 12 - 18 alkyl (hydroxyethyl) dimethyl ammonium compounds, particularly preferably from the corresponding hydrochloride salt of do.
본 발명의 조성물은 조성물의 총 중량을 기준으로 하여 0.5 중량% 내지 15 중량%의 양이온성 계면활성제를 함유할 수 있다.The compositions of the present invention may contain from 0.5% to 15% by weight of the cationic surfactant, based on the total weight of the composition.
계면활성제의 총량은 바람직하게는 1 내지 50 중량%, 특히 1 내지 40 중량%, 보다 특히 1 내지 30 중량%이다.The total amount of surfactant is preferably from 1 to 50% by weight, in particular from 1 to 40% by weight, more particularly from 1 to 30% by weight.
빌더 물질 B)Builder material B)
빌더 물질 B)로서는, 예를 들어 알칼리 금속 포스페이트, 특히 트리폴리포스페이트, 카르보네이트 및 히드로겐 카르보네이트, 특히 그의 나트륨 염, 실리케이트, 규산알루미늄, 폴리카르복실레이트, 폴리카르복실산, 유기 포스포네이트, 아미노알킬렌폴리(알킬렌포스포네이트) 및 이러한 화합물들의 혼합물이 고려된다.Builder materials B) include, for example, alkali metal phosphates, especially tripolyphosphates, carbonates and hydrogencarbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, Aminoalkylenepoly (alkylenephosphonates), and mixtures of such compounds are contemplated.
특히 적합한 실리케이트는 화학식 NaHSitO2t +1.pH2O 또는 Na2SitO2t +1.pH2O의 결정질 층상 실리케이트의 나트륨 염이며, 여기서 t는 1.9 내지 4의 수이고, p는 0 내지 20의 수이다.Particularly suitable silicates are the sodium salts of crystalline layered silicates of the formula NaHSi t O 2t +1. PH 2 O or Na 2 Si t O 2t +1 .pH 2 O, wherein t is a number from 1.9 to 4 and p is 0 To 20.
규산알루미늄 중에서는, 명칭 제올라이트 A, B, X 및 HS 하에 상업적으로 입수가능한 것들, 및 또한 2종 이상의 이러한 성분들을 포함하는 혼합물이 바람직하다. 제올라이트 A가 특히 바람직하다.Among the aluminum silicates, those which are commercially available under the names Zeolites A, B, X and HS and also mixtures comprising at least two such components are preferred. Zeolite A is particularly preferred.
폴리카르복실레이트 중에서는, 폴리히드록시카르복실레이트, 특히 시트레이트 및 아크릴레이트, 및 또한 그와 말레산 무수물과의 공중합체가 바람직하다. 바람직한 폴리카르복실산은 라세미 형태 또는 거울상이성질체적으로 순수한 (S,S) 형태의 니트릴로트리아세트산, 에틸렌디아민테트라아세트산 및 에틸렌디아민 디숙시네이트이다.Of the polycarboxylates, polyhydroxycarboxylates, especially citrates and acrylates, and also copolymers thereof with maleic anhydride are preferred. Preferred polycarboxylic acids are the racemic or enantiomerically pure (S, S) forms of nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate.
특히 적합한 포스포네이트 또는 아미노알킬렌폴리(알킬렌포스포네이트)는 1-히드록시에탄-1,1-디포스폰산, 니트릴로트리스(메틸렌포스폰산), 에틸렌디아민테트라메틸렌포스폰산 및 디에틸렌트리아민펜타메틸렌포스폰산의 알칼리 금속 염, 및 또한 그의 염이다. 또한 바람직한 폴리포스포네이트는 하기 화학식을 갖는다:Particularly suitable phosphonates or aminoalkylene poly (alkylene phosphonates) are 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid), ethylenediamine tetramethylenephosphonic acid and diethylene Alkali metal salts of triamine pentamethylene phosphonic acid, and also salts thereof. Also preferred polyphosphonates have the formula:
상기 식에서,In this formula,
R18은 CH2PO3H2 또는 그의 수용성 염이고,R 18 is CH 2 PO 3 H 2 or a water soluble salt thereof,
d는 값 0, 1, 2 또는 3의 정수이다.d is an integer having a value of 0, 1, 2 or 3.
특히 바람직한 것은 b가 값 1의 정수인 폴리포스포네이트이다.Particularly preferred is a polyphosphonate wherein b is an integer of value 1.
퍼옥시드 성분 C)Peroxide component C)
퍼옥시드 성분 C)로서는, 수용액 중에서 과산화수소를 생성할 수 있는 모든 화합물, 예를 들어 통상의 세척 온도, 예컨대 10 내지 95℃에서 텍스타일 물질을 표백하는, 문헌에 공지되어 있고 상업적으로 입수가능한 유기 및 무기 퍼옥시드가 고려된다. 그러나, 바람직하게는 무기 퍼옥시드, 예를 들어 퍼술페이트, 퍼보레이트, 퍼카르보네이트 및/또는 퍼실리케이트가 사용된다.Peroxide component C) includes all compounds capable of producing hydrogen peroxide in an aqueous solution, such as organic and inorganic compounds known in the literature and which are known in the literature for bleaching textile materials at conventional cleaning temperatures, e.g., Peroxides are considered. However, preference is given to using inorganic peroxides, such as persulfates, perborates, percarbonates and / or persilicates.
모든 이들 퍼옥시 화합물은 단독으로 또는 퍼옥시산 표백 전구체 및/또는 표백 촉매와 함께 이용될 수 있다. 퍼옥시산 전구체는 종종 표백 활성화제로 지칭된다. 적합한 표백 활성화제는 O- 및/또는 N-아실 기 및/또는 비치환 또는 치환된 벤조일 기를 보유하는 표백 활성화제를 포함한다. 바람직한 것은 폴리아실화 알킬렌디아민, 특히 테트라아세틸에틸렌디아민 (TAED); 아실화 글리콜우릴, 특히 테트라아세틸 글리콜 우레아 (TAGU), N,N-디아세틸-N,N-디메틸우레아 (DDU); 소듐-4-벤조일옥시 벤젠 술포네이트 (SBOBS); 소듐-1-메틸-2-벤조일옥시 벤젠-4-술포네이트; 소듐-4-메틸-3-벤조일옥시 벤조에이트; 트리메틸 암모늄 톨루일옥시-벤젠 술포네이트; 아실화 트리아진 유도체, 특히 1,5-디아세틸-2,4-디옥소헥사히드로-1,3,5-트리아진 (DADHT); 화학식 6의 화합물:All these peroxy compounds can be used alone or in combination with peroxyacid bleaching precursors and / or bleach catalysts. Peroxy acid precursors are often referred to as bleach activators. Suitable bleach activators include bleach activators having O- and / or N-acyl groups and / or unsubstituted or substituted benzoyl groups. Preferred are polyarylated alkylenediamines, especially tetraacetylethylenediamine (TAED); Acylated glycolurils, especially tetraacetyl glycol urea (TAGU), N, N-diacetyl-N, N-dimethylurea (DDU); Sodium-4-benzoyloxybenzenesulfonate (SBOBS); Sodium-1-methyl-2-benzoyloxybenzene-4-sulfonate; Sodium-4-methyl-3-benzoyloxybenzoate; Trimethylammonium toluyloxy-benzenesulfonate; Acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); The compound of formula 6:
(상기 식에서, R22는 술포네이트 기, 카르복실산 기 또는 카르복실레이트 기이고, 여기서 R21은 선형 또는 분지형 (C7-C15)알킬임), 특히 명칭 SNOBS, SLOBS 및 DOBA 하에 공지된 활성화제이며; 또한 퍼옥시드를 사용하여 퍼이민산을 형성시킨 니트릴 화합물이 표백 활성화제로서 고려된다. 이러한 표백 활성화제는 조성물의 총 중량을 기준으로 하여 12 중량% 이하, 바람직하게는 2-10 중량%의 양으로 사용될 수 있다.Wherein R 22 is a sulfonate group, a carboxylic acid group or a carboxylate group, wherein R 21 is a linear or branched (C 7 -C 15 ) alkyl, especially under the names SNOBS, SLOBS and DOBA ≪ / RTI > Also, nitrile compounds in which perimic acid is formed using peroxide are considered as bleaching activators. Such a bleach activator may be used in an amount of 12 wt% or less, preferably 2-10 wt%, based on the total weight of the composition.
통상적으로 공지된 추가의 표백 촉매, 예를 들어 EP 1194514, EP 1383857 또는 WO04/007657에 개시된 바와 같은 전이 금속 착체를 사용하는 것이 또한 가능하다.It is also possible to use transition metal complexes as disclosed in commonly known further bleaching catalysts, for example EP 1194514, EP 1383857 or WO 04/007657.
추가의 표백 촉매는 US 2001044401, EP 0458397, WO 9606154, EP 1038946, EP 0900264, EP 0909809, EP 1001009, WO 9965905, WO 0248301, WO 0060045, WO 02077145, WO 0185717, WO 0164826, EP 0923635, DE 19639603, DE102007017654, DE102007017657, DE102007017656, US 20030060388, EP 0918840B1, EP 1174491A2, EP 0805794B1, WO 9707192A1, US 6235695B1, EP 0912690B1, EP 832969B1, US 6479450B1, WO 9933947A1, WO 0032731A1, WO 03054128A1, DE102004003710, EP 1083730, EP 1148117, EP 1445305, US 6476996, EP 0877078, EP 0869171, EP 0783035, EP 0761809 및 EP 1520910에 개시되어 있다.Additional bleaching catalysts are described in US 2001044401, EP 0458397, WO 9606154, EP 1038946, EP 0900264, EP 0909809, EP 1001009, WO 9965905, WO 0248301, WO 0060045, WO 02077145, WO 0185717, WO 0164826, EP 0923635, DE 19639603, EP 1 070 717 B1, EP 1 0 0 0 7 0 1 1, WO 03054128A1, DE 10 2004003710, EP 1083730, EP 1148117, EP 1 0707176, DE 10-2007017654, DE 10-2007017656, US 20030060388, EP 0918840B1, EP 1174491A2, EP 0805794B1, WO 9707192A1, US6235695B1, EP 0912690B1, EP 0932691B1, EP 832969B1, US 6479450B1, WO 9933947A1, WO 0032731A1, EP 1445305, US 6476996, EP 0877078, EP 0869171, EP 0783035, EP 0761809 and EP 1520910.
조성물은, 본 발명에 따른 조합 이외에, 예를 들어 비스-트리아지닐아미노-스틸벤디술폰산, 비스-트리아졸릴-스틸벤디술폰산, 비스-스티릴-비페닐 또는 비스-벤조푸라닐비페닐, α 비스-벤족살릴 유도체, 비스-벤즈이미다졸릴 유도체 또는 쿠마린 유도체 또는 피라졸린 유도체 부류로부터의 1종 이상의 광학 증백제를 포함할 수 있다.The composition may also contain, in addition to the combinations according to the invention, for example, bis-triazinylamino-stilbenylsulfonic acid, bis-triazolyl-stilbenylsulphonic acid, bis- styryl-biphenyl or bis- Benzyl salicyl derivatives, bis-benzimidazolyl derivatives or coumarin derivatives, or pyrazoline derivative classes.
조성물은 또한 1종 이상의 추가의 첨가제를 포함할 수 있다. 이러한 첨가제는, 예를 들어 오물-현탁화제, 예를 들어 소듐 카르복시메틸셀룰로스이고; pH 조절제, 예를 들어 알칼리 금속 또는 알칼리 토금속 실리케이트; 거품 조절제, 예를 들어 비누; 분무 건조 및 과립화 특성의 조절을 위한 염, 예를 들어 황산나트륨; 퍼퓸; 및 또한 적절한 경우에 대전방지제 및 연화제, 예컨대 스멕타이트; 표백제; 안료; 및/또는 토닝제이다. 이들 구성성분은 특히 이용되는 어떠한 표백제에 대해서도 안정해야 한다.The composition may also include one or more additional additives. Such additives are, for example, soil-suspending agents, for example sodium carboxymethylcellulose; pH adjusting agents, such as alkali metal or alkaline earth metal silicates; Foam control agents, for example soaps; Salts for controlling spray drying and granulation properties, such as sodium sulfate; Perfume; And also where appropriate, antistatic agents and softening agents such as smectites; bleach; Pigments; And / or a toning agent. These components should be stable, especially for any bleaching agent used.
이러한 보조제가 사용되는 경우에, 이들은 세제 제제의 총 중량을 기준으로 하여 0.1 - 20 중량%, 바람직하게는 0.5 - 10 중량%, 특히 0.5 - 5 중량%의 총량으로 첨가된다.When such adjuvants are used, they are added in a total amount of from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight, based on the total weight of the detergent formulation.
또한, 세제는 또한 효소를 임의로 포함할 수 있다. 효소는 얼룩 제거를 위해 첨가될 수 있다. 통상적으로 효소는, 예를 들어 혈액, 우유, 풀 또는 과일 주스와 같은 단백질 또는 전분으로 인한 얼룩에 대한 작용을 개선한다. 바람직한 효소는 셀룰라제 및 프로테아제, 특히 프로테아제이다. 셀룰라제는 셀룰로스 및 그의 유도체와 반응하여 이들을 가수분해시켜 글루코스, 셀로비오스 및 셀로올리고사카라이드를 형성하는 효소이다. 셀룰라제는 오물을 제거하고, 또한 직물의 유연한 촉감을 증진시키는 효과를 갖는다.The detergent may also optionally comprise an enzyme. Enzymes can be added for spot removal. Enzymes typically improve the action on stains due to proteins or starches, such as, for example, blood, milk, grass or fruit juice. Preferred enzymes are cellulases and proteases, in particular proteases. Cellulases are enzymes that react with cellulose and its derivatives to hydrolyze them to form glucose, cellobiose and cellulosic sacides. Cellulases have the effect of removing dirt and also promoting the soft touch of the fabric.
통상적인 효소의 예는 비제한적으로 다음을 포함한다:Examples of conventional enzymes include, but are not limited to:
US 6,242,405, 칼럼 14, 라인 21 내지 32에 기재된 바와 같은 프로테아제;Proteases as described in US 6,242,405, column 14, lines 21 to 32;
US 6,242,405, 칼럼 14, 라인 33 내지 46에 기재된 바와 같은 리파제;Lipases as described in US 6,242, 405, column 14, lines 33 to 46;
US 6,242,405, 칼럼 14, 라인 47 내지 56에 기재된 바와 같은 아밀라제; 및Amylase as described in US 6,242,405, column 14, lines 47 to 56; And
US 6,242,405, 칼럼 14, 라인 57 내지 64에 기재된 바와 같은 셀룰라제;Cellulases as described in US 6,242,405, column 14, lines 57 to 64;
상업적으로 입수가능한 세제 프로테아제, 예컨대 알칼라제(Alcalase)®, 에스페라제(Esperase)®, 에버라제(Everlase)®, 사비나제(Savinase)®, 칸나제(Kannase)® 및 듀라짐(Durazym)® (예를 들어 노보자임스 에이/에스(NOVOZYMES A/S)에 의해 시판됨);Commercially available detergent proteases such as Alcalase®, Esperase®, Everlase®, Savinase®, Kannase®, and Durazym®, (Commercially available, for example, by NOVOZYMES A / S);
상업적으로 입수가능한 세제 아밀라제, 예컨대 테르마밀(Termamyl)®, 듀라밀(Duramyl)®, 스테인자임(Stainzyme)®, 나탈라제(Natalase)®, 반(Ban)® 및 펀가밀 (Fungamyl)® (예를 들어 노보자임스 에이/에스에 의해 시판됨);Commercially available detergent amylases such as Termamyl®, Duramyl®, Stainzyme®, Natalase®, Ban® and Fungamyl® For example, marketed by Novozymes A / S);
상업적으로 입수가능한 세제 셀룰라제, 예컨대 셀루자임(Celluzyme)®, 케어자임 (Carezyme)® 및 엔돌라제(Endolase)® (예를 들어 노보자임스 에이/에스에 의해 시판됨);Commercially available detergent cellulases such as Celluzyme®, Carezyme® and Endolase® (commercially available, for example, by Novozymes A / S);
상업적으로 입수가능한 세제 리파제, 예컨대 리포라제(Lipolase)®, 리포라제 울트라(Lipolase Ultra)® 및 리포프라임(Lipoprime)® (예를 들어, 노보자임스 에이/에스에 의해 시판됨);Commercially available detergent lipases such as Lipolase®, Lipolase Ultra® and Lipoprime® (eg, sold by Novozymes A / S);
적합한 만난아제, 예컨대 만난어웨이(Mannanaway)® (노보자임스 에이/에스에 의해 시판됨).Suitable mannanases, such as Mannanaway® (available from Novozymes A / S).
효소는, 사용되는 경우에, 세제 제제의 총 중량을 기준으로 하여 0.01 내지 5 중량%, 특히 0.05 내지 5 중량%, 보다 특히 0.1 내지 4 중량%의 총량으로 존재할 수 있다.The enzyme, if used, may be present in a total amount of 0.01 to 5% by weight, especially 0.05 to 5% by weight, more particularly 0.1 to 4% by weight, based on the total weight of the detergent formulation.
본 발명에 따른 조성물을 위한 추가의 바람직한 첨가제는, 텍스타일의 세척 동안, 세척 조건 하에 텍스타일로부터 방출된 세척액 중의 염료로 인한 얼룩을 방지하는 염료-고정 작용제 및/또는 중합체이다. 이러한 중합체는 바람직하게는 음이온성 또는 양이온성 치환기의 도입에 의해 개질된 것일 수도 있는 폴리비닐피롤리돈, 폴리비닐이미다졸 또는 폴리비닐피리딘-N-옥시드, 특히 5000 내지 60,000 범위, 보다 특히 10,000 내지 50,000 범위의 분자량을 갖는 것들이다. 이러한 중합체가 사용되는 경우에, 이들은 세제 제제의 총 중량을 기준으로 하여 통상적으로 0.01 내지 5 중량%, 특히 0.05 내지 5 중량%, 보다 특히 0.1 내지 2 중량%의 총량으로 사용된다. 바람직한 중합체는 WO-A-02/02865 (특히 1 페이지, 마지막 단락 및 2 페이지, 첫번째 단락 참조)에 언급된 것들 및 WO-A-04/05688에 언급된 것들이다.A further preferred additive for the composition according to the invention is a dye-fixing agent and / or polymer which prevents staining due to the dye in the washing liquid released from the textile under washing conditions during washing of the textile. Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine-N-oxides which may be modified by introduction of anionic or cationic substituents, in particular in the range of from 5000 to 60,000, Those having a molecular weight in the range of 10,000 to 50,000. When such polymers are used, they are usually used in a total amount of from 0.01 to 5% by weight, in particular from 0.05 to 5% by weight, more particularly from 0.1 to 2% by weight, based on the total weight of the detergent formulation. Preferred polymers are those mentioned in WO-A-02/02865 (especially page 1, last paragraph and page 2, first paragraph) and those mentioned in WO-A-04/05688.
본원에서 본 발명의 조성물은 또한 1종 이상의 중금속 킬레이트화제, 예컨대 히드록시에틸디포스포네이트 (HEDP)를 임의로 함유할 수 있다. 보다 일반적으로, 본원에서 사용하기에 적합한 킬레이트화제는 아미노 카르복실레이트, 아미노 포스포네이트, 다관능성-치환된 방향족 킬레이트화제 및 그의 혼합물로 이루어진 군으로부터 선택될 수 있다. 본원에서 사용하기에 적합한 다른 킬레이트화제는 상업용 데퀘스트(DEQUEST) 시리즈 및 날코, 인크(Nalco, Inc)의 킬레이트화제이다.The composition of the present invention herein may also optionally contain one or more heavy metal chelating agents such as hydroxyethyl diphosphonate (HEDP). More generally, suitable chelating agents for use herein may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctional-substituted aromatic chelating agents, and mixtures thereof. Other chelating agents suitable for use herein are the commercial DEQUEST series and chelating agents of Nalco, Inc.
임의적 킬레이트화제로서 유용한 아미노카르복실레이트는 에틸렌디아민테트라아세테이트, N-히드록시에틸에틸렌디아민트리아세테이트, 니트릴로트리아세테이트, 에틸렌디아민 테트라프로피오네이트, 트리에틸렌테트라아민헥사아세테이트, 디에틸렌트리아민-펜타아세테이트 및 에탄올디글리신, 그의 알칼리 금속, 암모늄 및 치환된 암모늄 염, 및 그의 혼합물을 포함한다.Aminocarboxylates useful as optional chelating agents include, but are not limited to, ethylenediaminetetraacetate, N-hydroxyethylethylenediamine triacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetraamine hexaacetate, diethylenetriamine- And ethanol diglycine, alkali metal, ammonium and substituted ammonium salts thereof, and mixtures thereof.
아미노포스포네이트는 세제 조성물 중에서 전체 인의 적어도 낮은 수준이 허용되는 경우에 본 발명의 조성물 중에서 킬레이트화제로서 사용하기에 또한 적합하며, 에틸렌디아민테트라키스 (메틸렌포스포네이트)를 포함한다.Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention where at least a low level of total phosphorus is permitted in the detergent composition, including ethylenediaminetetrakis (methylenephosphonate).
추가의 생분해성 격리제는, 예를 들어 아미노산 아세테이트, 예컨대 트릴론(Trilon) M (바스프(BASF)) 및 디졸빈(Dissolvine) GL (악조(AKZO)), 및 또한 아스파라긴산 유도체, 예컨대 베이퓨어(Baypure) CX이다.Additional biodegradable sequestrants include, for example, amino acid acetates such as Trilon M (BASF) and Dissolvine GL (AKZO), and also aspartic acid derivatives such as Bay Pure Baypure) CX.
바람직하게는, 아미노포스포네이트는 약 6개 초과의 탄소 원자를 갖는 알킬 또는 알케닐 기를 함유하지 않는다.Preferably, the aminophosphonate contains no alkyl or alkenyl groups having more than about 6 carbon atoms.
본원에서 사용하기에 매우 바람직한 생분해성 킬레이트화제는 에틸렌디아민 디숙시네이트("EDDS")이다.A highly preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate ("EDDS").
이용되는 경우에, 이들 킬레이트화제 또는 전이-금속 선택적 격리제는 본원의 세탁 세제 제제 중 일반적으로 약 0.001 중량% 내지 약 10 중량%, 보다 바람직하게는 약 0.05 중량% 내지 약 1 중량%를 차지할 것이다.If utilized, these chelating or transition-metal selective quenchers will generally comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1%, by weight of the laundry detergent formulations herein .
본원에서 바람직한 조성물은 분산제 중합체를 추가로 함유할 수 있다. 존재하는 경우에, 분산제 중합체는 세제 조성물 중 전형적으로 0 중량% 내지 약 25 중량%, 바람직하게는 약 0.5 중량% 내지 약 20 중량%, 보다 바람직하게는 약 1 중량% 내지 약 8 중량% 범위의 수준이다.A preferred composition herein may further comprise a dispersant polymer. When present, the dispersant polymer is typically present in the detergent composition in an amount ranging from 0% to 25% by weight, preferably from about 0.5% to about 20% by weight, more preferably from about 1% to about 8% Level.
적합한 중합체는 바람직하게는 적어도 부분적으로 중화되거나 또는 폴리카르복실산의 알칼리 금속, 암모늄 또는 치환된 암모늄 (예컨대 모노-, 디- 또는 트리에탄올암모늄) 염이다. 알칼리 금속, 특히 나트륨 염이 가장 바람직하다. 중합체의 분자량은 넓은 범위에 걸쳐 변화할 수 있지만, 이는 바람직하게는 약 1,000 내지 약 500,000, 보다 바람직하게는 약 1,000 내지 약 250,000이다.Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g. mono-, di- or triethanolammonium) salts of polycarboxylic acids. Most preferred are alkali metals, especially sodium salts. The molecular weight of the polymer can vary over a wide range, but it is preferably from about 1,000 to about 500,000, more preferably from about 1,000 to about 250,000.
중합되어 적합한 분산제 중합체를 형성할 수 있는 불포화 단량체 산은 아크릴산, 말레산 (또는 말레산 무수물), 푸마르산, 이타콘산, 아코니트산, 메사콘산, 시트라콘산 및 메틸렌말론산을 포함한다. 메틸 비닐 에테르, 스티렌, 에틸렌 등과 같이 카르복실레이트 라디칼을 함유하지 않는 단량체 분절의 존재는, 이러한 분절이 분산제 중합체 중 약 50 중량% 초과를 구성하지 않는 한 적합하다.Unsaturated monomer acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene malonic acid. The presence of monomeric segments that do not contain carboxylate radicals, such as methyl vinyl ether, styrene, ethylene, and the like, is suitable unless such segments constitute more than about 50 weight percent of the dispersant polymer.
약 3,000 내지 약 100,000, 바람직하게는 약 4,000 내지 약 20,000의 분자량 및 분산제 중합체 중 약 50 중량% 미만, 바람직하게는 약 20 중량% 미만의 아크릴아미드 함량을 갖는 아크릴아미드 및 아크릴레이트의 공중합체가 또한 사용될 수 있다. 가장 바람직하게는, 이러한 분산제 중합체는 약 4,000 내지 약 20,000의 분자량 및 중합체의 총 중량을 기준으로 하여 약 0 중량% 내지 약 15 중량%의 아크릴아미드 함량을 갖는다.Copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50% by weight, and preferably less than about 20% by weight of the dispersant polymer, Can be used. Most preferably, such a dispersant polymer has a molecular weight of about 4,000 to about 20,000 and an acrylamide content of about 0 wt% to about 15 wt%, based on the total weight of the polymer.
특히 바람직한 분산제 중합체는 저분자량의 개질된 폴리아크릴레이트 공중합체이다. 이러한 공중합체는 단량체 단위로서 a) 약 90 중량% 내지 약 10 중량%, 바람직하게는 약 80 중량% 내지 약 20 중량%의 아크릴산 또는 그의 염, 및 b) 약 10 중량% 내지 약 90 중량%, 바람직하게는 약 20 중량% 내지 약 80 중량%의 치환된 아크릴 단량체 또는 그의 염을 함유하고, 화학식: -[(C(Ra')C(Rb')(C(O)ORc')]을 가지며, 여기서 외관상 채워지지 않은 원자가는 사실상 수소에 의해 점유되고, 치환기 Ra', Rb' 또는 Rc', 바람직하게는 Ra' 또는 Rb' 중 적어도 1개는 탄소수 1 내지 4의 알킬 또는 히드록시알킬 기이고; Ra' 또는 Rb'은 수소일 수 있고, Rc'은 수소 또는 알칼리 금속 염일 수 있다. Ra'이 메틸이고, Rb'이 수소이고, Rc'이 나트륨인 치환된 아크릴 단량체가 가장 바람직하다.Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. Such copolymers may comprise as monomer units a) from about 90% to about 10% by weight, preferably from about 80% to about 20% by weight of acrylic acid or its salt, and b) from about 10% to about 90% preferably it contains a substituted acrylic monomer or its salt of from about 20% to about 80% by weight, the formula: - [(C (R a ') C (R b') (C (O) oR c ') Wherein at least one of the substituents R a ' , R b', or R c ' , preferably R a' or R b ' , is occupied by hydrogen, R a ' is methyl, R b' is hydrogen, and R c ' is an alkyl or hydroxyalkyl group of the formula: R a' or R b ' may be hydrogen and R c' may be hydrogen or an alkali metal salt. Most preferred are substituted acrylic monomers which are ' disodium.
바람직하게는, 적합한 저분자량의 폴리아크릴레이트 분산제 중합체는 약 15,000 미만, 바람직하게는 약 500 내지 약 10,000, 가장 바람직하게는 약 1,000 내지 약 5,000의 분자량을 갖는다. 본원에서 사용하기에 가장 바람직한 폴리아크릴레이트 공중합체는 약 3,500의 분자량을 갖고 약 70 중량% 아크릴산 및 약 30 중량% 메타크릴산을 포함하는 중합체의 완전 중화 형태이다.Preferably, a suitable low molecular weight polyacrylate dispersant polymer has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, and most preferably from about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein is a fully neutralized form of a polymer having a molecular weight of about 3,500 and comprising about 70 wt% acrylic acid and about 30 wt% methacrylic acid.
본원에서 유용한 다른 분산제 중합체는 약 950 내지 약 30,000의 분자량을 갖는 폴리에틸렌 글리콜 및 폴리프로필렌 글리콜을 포함한다.Other dispersant polymers useful herein include polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000.
본원에서 유용한 또 다른 분산제 중합체는 셀룰로스 술페이트 에스테르, 예컨대 셀룰로스 아세테이트 술페이트, 셀룰로스 술페이트, 히드록시에틸 셀룰로스 술페이트, 메틸셀룰로스 술페이트 및 히드록시프로필셀룰로스 술페이트를 포함한다. 소듐 셀룰로스 술페이트는 상기 군 중 가장 바람직한 중합체이다.Still other dispersant polymers useful herein include cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethylcellulose sulfate, methylcellulose sulfate and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of the above group.
다른 적합한 분산제 중합체는 카르복실화 폴리사카라이드, 특히 전분, 셀룰로스 및 알기네이트이다.Other suitable dispersant polymers are carboxylated polysaccharides, especially starch, cellulose and alginate.
허용되는 분산제의 또 다른 군은 유기 분산제 중합체, 예컨대 폴리아스파르테이트이다.Another group of acceptable dispersants are organic dispersant polymers, such as polyaspartates.
본 발명에 따른 세정 제제에 사용될 수 있는 유기 용매는, 특히 세정 제제가 액체 또는 페이스트 형태인 경우에, 1 내지 4개의 탄소 원자를 갖는 알콜, 특히 메탄올, 에탄올, 이소프로판올 및 tert-부탄올, 2 내지 4개의 탄소 원자를 갖는 디올, 특히 에틸렌 글리콜 및 프로필렌 글리콜, 및 그의 혼합물, 및 언급된 부류의 화합물로부터 유도가능한 에테르를 포함한다. 이러한 수혼화성 용매는 본 발명에 따른 세정 제제 중에 바람직하게는 20 중량%를 초과하지 않는 양, 특히 1 중량% 내지 15 중량%의 양으로 존재한다.The organic solvents which can be used in the cleaning preparations according to the invention are, in particular in the case of liquid or paste formulations, alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, 2-4 Diols with carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof, and ethers derivable from the classes of compounds mentioned. Such water-miscible solvents are preferably present in amounts not exceeding 20% by weight, in particular in amounts of from 1% to 15% by weight, in the cleaning formulation according to the invention.
세제 제제는, 예를 들어 분말 과립, 정제 (정), 겔 및 액체와 같은 다양한 물리적 형상을 취할 수 있다. 그의 예는, 특히 통상의 고성능 세제 분말, 초압축형 고성능 세제 분말, 통상의 중질 액체 세제, 고농축 겔 및 정을 포함한다.Detergent formulations can take a variety of physical forms such as, for example, powdered granules, tablets (tablets), gels and liquids. Examples thereof include, in particular, conventional high-performance detergent powders, ultra-compressible high-performance detergent powders, conventional heavy liquid detergents, highly concentrated gels and tablets.
세제 제제는 또한 5 중량% 내지 90 중량%, 바람직하게는 10 중량% 내지 70 중량%의 물을 함유하는 수성 액체의 형태, 또는 5 중량% 미만, 바람직하게는 0 중량% 내지 1 중량%의 물을 함유하는 비-수성 액체의 형태일 수 있다. 비-수성 액체 세제 제제는 다른 용매를 담체로서 포함할 수 있다. 저분자량의 1급 또는 2급 알콜, 예를 들어 메탄올, 에탄올, 프로판올 및 이소프로판올이 이러한 목적에 적합하다. 사용되는 가용화 계면활성제는 바람직하게는 모노히드록시 알콜이지만, 폴리올, 예컨대 2 내지 6개의 탄소 원자 및 2 내지 6개의 히드록시 기를 함유하는 것들 (예를 들어, 1,3-프로판디올, 에틸렌 글리콜, 글리세롤 및 1,2-프로판디올)도 또한 사용될 수 있다. 이러한 담체는 세제 제제의 총 중량을 기준으로 하여 통상적으로 5 중량% 내지 90 중량%, 바람직하게는 10 중량% 내지 50 중량%의 총량으로 사용된다. 세제 제제는 또한 소위 "단위 액체 용량" 형태로 사용될 수도 있다.Detergent formulations may also be in the form of an aqueous liquid containing from 5% to 90%, preferably from 10% to 70% by weight of water, or in the form of an aqueous liquid containing less than 5% by weight, preferably from 0% to 1% In the form of a non-aqueous liquid. Non-aqueous liquid detergent formulations may include other solvents as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable for this purpose. The solubilizing surfactants used are preferably monohydroxy alcohols, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (for example, 1,3-propanediol, ethylene glycol, Glycerol and 1,2-propanediol) can also be used. Such carriers are typically used in a total amount of 5% to 90% by weight, preferably 10% to 50% by weight, based on the total weight of the detergent formulation. Detergent formulations may also be used in the so-called "unit liquid capacity" form.
상기 주어진 정의 및 바람직한 것은 본 발명의 모든 측면에 대해 동등하게 적용된다.The above definitions and preferred are equally applicable to all aspects of the invention.
하기 실시예는 본 발명을 예시한다.The following examples illustrate the invention.
약어 및 시약:Abbreviations and Reagents:
GPC: 겔 투과 크로마토그래피GPC: gel permeation chromatography
PS-표준물: GPC 보정을 위한 폴리스티렌 표준물PS-standard: Polystyrene standard for GPC calibration
mbara = 밀리바 절대 압력mbara = millibars absolute pressure
SC = 할로겐 건조기 메틀러 톨레도(Halogen dryer Mettler Toledo) (150℃에서, 0.5 g 샘플)에 의한 고체 함량 측정값. (결과는 중량%로서 수득됨).SC = Halogen dryer Measured value of solids content by Halogen dryer Mettler Toledo (0.5 g sample at 150 ° C). (Results obtained as% by weight).
THF: 테트라히드로푸란THF: tetrahydrofuran
EtOH: 에탄올EtOH: ethanol
MeOH: 메탄올MeOH: methanol
TFAA: 트리플루오로아세트산 무수물TFAA: Trifluoroacetic anhydride
PTSA: 파라-톨루엔술폰산 1수화물PTSA: Para-toluenesulfonic acid monohydrate
MPA: 1-메톡시-2-프로필 아세테이트MPA: 1-Methoxy-2-propyl acetate
n-BA: n-부틸아크릴레이트n-BA: n-butyl acrylate
PD: 다분산도 (샘플의 다분산도는 중량 평균 분자량 Mw를 Mn으로 나눈 것으로 정의되며, 분포가 얼마나 좁은지에 대한 표시를 제공함)PD: polydispersity (the polydispersity of the sample is defined as the weight average molecular weight Mw divided by Mn and provides an indication of how narrow the distribution is)
4VP: 스케넥터디 인터내셔널(Schenectady International)사로부터 입수가능한 4-비닐피리딘4VP: 4-vinylpyridine available from Schenectady International
세틸알콜 (코그니스(Cognis)사로부터 입수가능한 98% 순도 1-헥사데칸올)Cetyl alcohol (98% pure 1-hexadecanol available from Cognis)
리알(LIAL)® 125 A: 사솔 올레핀즈 앤드 서팩턴츠 게엠베하(Sasol Olefins and Surfactants GmbH)로부터의 직쇄 및 모노-분지형 C12 - 15알칸올들의 혼합물.Rial (LIAL) ® 125 A: Sasol olefins's end seopaek teoncheu geem beha (Sasol Olefins and Surfactants GmbH) straight chain and mono from - branched C 12 - 15 mixture of alkanols.
LuN400: 루프라겐(Lupragen)® N 400: 바스프사로부터 입수가능한 N,N',N"- 트리메틸아미노에틸에탄올아민LuN400: Lupragen® N 400: N, N ', N "-trimethylaminoethylethanolamine available from BASF Corp.
PCL1075: 1075 g/mol의 Mn을 갖는 폴리카프로락톤 알파-세틸옥시-, 오메가-히드록시-PCL1075: Polycaprolactone alpha-cetyloxy-, omega-hydroxy- < RTI ID = 0.0 >
LuON70: 루텐솔(Lutensol)® ON 70 (바스프사로부터 입수가능한 466 g/mol의 Mn을 갖는 폴리에틸렌 글리콜 모노-이소데실에테르)LuON70: Lutensol 占 ON 70 (polyethylene glycol mono-isodecyl ether with Mn of 466 g / mol available from BASF)
MPEG500 (클라리언트(Clariant)사로부터 입수가능한 500 g/mol의 Mn을 갖는 폴리 에틸렌 글리콜 모노메틸에테르)MPEG 500 (polyethyleneglycol monomethyl ether with Mn of 500 g / mol available from Clariant)
솔케탈(Solketal): 이소프로필리덴 기 보호된 글리세롤, (+/-)-2,2-디메틸-4-히드록시메틸-1,3-디옥솔란의 라세미 혼합물Solketal: racemic mixture of isopropylidene-group protected glycerol, (+/-) - 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane
HEMO: N-히드록시에틸모르폴린HEMO: N-hydroxyethylmorpholine
LitOBu: 알드리치 인크(Aldrich Inc)로부터 입수가능한 리튬-tert부톡실레이트LithOBU: Lithium-tert-butoxylate available from Aldrich Inc
도웩스(DOWEX) 50WX8은 다우(DOW)사로부터 입수가능한 산 이온 교환 수지이다. 도웩스를 활성화시키기 위해, 이를 2% HCl 용액 중에 밤새 침지한 다음, 여과하고, 물로 세척하고, 오븐 중에서 80℃에서 건조시켰다.DOWEX 50WX8 is an acid ion exchange resin available from DOW. To activate Dowex, it was soaked in 2% HCl solution overnight, then filtered, washed with water and dried at 80 ° C in an oven.
NOR 01: GB 2335190에 따라 제조된 중합 조절제.NOR 01: polymerization modifier prepared according to GB 2335190.
에스테르교환에 의해 수득되는, nBA의 제어 자유 라디칼 중합을 기초로 한 빗살형-공중합체의 일반적인 이상화된 구조:Generalized idealized structure of a comb-type copolymer based on controlled free radical polymerization of nBA, obtained by transesterification:
에스테르교환은 랜덤하게 진행시켰다. 이는 다수의 화학식에 의해서도 적절하게 반영되지 않으며, 이에 따라 부틸 에스테르의 블록 및 다른 에스테르 (R1 내지 R6)의 블록이 있는 것으로 보일 것이다. 상기 화학식은 에스테르가 랜덤하게 존재하는 것을 의미하고, 지수는 각각의 에스테르의 대략적인 몰량을 나타낸다. 그러나, 약칭, 예를 들어 실시예 A1의 폴리(n-BA-co-MPEG500A)은, 중합체의 양측 상의 말단기, 즉 상기 화학식에 나타낸 바와 같은 1-페닐-에틸 기 및 NOR 단편을 언급하지 않는다는 것에 주의해야 한다. 약칭에서의 표시 -co-는 중합체를 형식적으로 구성하는 단량체, 예를 들어 n-BA 및 MPEG500-아크릴레이트가 랜덤하게 존재하는 것을 나타낸다.The ester exchange was carried out at random. This is not adequately reflected by many of the formulas, and thus will appear to be blocks of butyl esters and blocks of other esters (R 1 to R 6). The above formula means that the ester is present at random, and the index indicates the approximate molar amount of each ester. However, abbreviations, for example poly (n-BA-co-MPEG500A) of Example A1, do not refer to the terminal groups on both sides of the polymer, i.e. the 1-phenyl-ethyl group and the NOR fragment as shown in the above formula Care should be taken. The designation -co- in the abbreviation indicates that monomers constituting the polymer formally, for example, n-BA and MPEG 500-acrylate are present at random.
실시예 B3, 폴리(nBA-b-4VP)에 나타낸 바와 같은 표시 -b-는 중합체가 2개의 정의된 블록, n-BA 단량체 단위의 제1 블록 및 4-비닐피리딘 단량체 단위의 제2 블록으로 구성되는 것을 의미한다.The indication -b- as shown in Example B3, poly (nBA-b-4VP), indicates that the polymer is composed of two defined blocks, a first block of n-BA monomer units and a second block of 4-vinylpyridine monomer units .
LCST-형 용액 거동LCST-type solution behavior
수득된 중합체가 물에 가용성인 경우에, 이는 LCST-형 용액 거동 (LCST = 하한 임계 용액 온도(lower critical solution temperature))를 나타낼 수 있으며, 즉 중합체의 용해도는 온도가 증가함에 따라 감소한다. 예를 들어 탈염수 중 최종 중합체의 1 중량% 용액은 실온에서 투명한 용액이지만, 예를 들어 50℃ (= LCST) 초과의 승온에서 혼탁해진다. 유사하게, 상기 관찰을 염 용액 (예를 들어 물 중 1% NaCl) 중에서 전형적으로는 수득된 중합체에 대해 수행할 수 있으며, 염 용액 중에서의 LCST는 탈염수 중에서보다 낮을 수 있다. RT 미만의 LCST를 갖는 중합체는 물 중에서 에멀젼으로서 수득되고, 85℃ 초과의 LCST를 갖는 중합체는 측정 전반에 걸쳐 투명한 용액으로 남아 있으며, 세척 용도에 중요한 범위 (RT 내지 90℃)에서 LCST를 나타내지 않는다. 표시 > 85℃는 85℃의 최대 측정 온도까지 LCST가 관찰되지 않은 것을 의미하며, 이는 용액이 85℃까지 투명하게 유지되는 것을 의미한다.If the polymer obtained is soluble in water, it may exhibit an LCST-type solution behavior (LCST = lower critical solution temperature), i.e. the solubility of the polymer decreases with increasing temperature. For example, a 1 wt% solution of the final polymer in demineralized water is a clear solution at room temperature, but becomes turbid at elevated temperatures, e.g., above 50 DEG C (= LCST). Similarly, the above observations may be performed on a polymer typically obtained in a salt solution (e.g., 1% NaCl in water), and the LCST in the salt solution may be lower than in desalted water. Polymers with an LCST below RT are obtained as an emulsion in water and polymers with an LCST above 85 DEG C remain a clear solution throughout the measurement and do not exhibit LCST in the range critical for cleaning applications (RT to 90 DEG C) . Indication> 85 ° C means no LCST observed to the maximum measured temperature of 85 ° C, which means that the solution remains clear to 85 ° C.
A) 중합체 및 공중합체의 제조A) Preparation of Polymers and Copolymers
실시예 B1: 선형 중합체 폴리(n-BA)의 합성Example B1: Synthesis of linear polymer poly (n-BA)
자기 교반 막대, 냉각기, 온도계, 적하 깔때기를 갖춘 3구 1000ml 둥근 바닥 플라스크 중에서, n-부틸아크릴레이트 150.10 g (n-BA, 128.2 g/mol), NOR 01 8.55 g (317.5 g/mol) 및 MPA 122.13 g을 첨가하고, N2/진공으로 3회 탈기시키고, 약 8 mol%의 전환율에 도달할 때까지 N2 하에 135℃에서 중합시켰다. 반응물에 n-BA 338.89 g을 적하 깔때기로 서서히 첨가하고, 약 48 mol%의 전환율 (SC 측정에 의함)에 도달할 때까지 N2 하에 135℃에서 중합시켰다. 잔류 단량체 및 용매를 80℃ 및 12 mbara에서 증류 제거하였다.(N-BA, 128.2 g / mol), NOR 01 8.55 g (317.5 g / mol) and MPA (n-butyl acrylate) in a three-necked 1000 ml round bottomed flask equipped with a magnetic stirrer, a condenser, a thermometer and a dropping funnel. 122.13 g was added, degassed N 2 / vacuum three times and polymerized at 135 ° C under N 2 until a conversion of about 8 mol% was reached. To the reaction was added 338.89 g of n-BA slowly to the dropping funnel and polymerized at 135 캜 under N 2 until a conversion of about 48 mol% (by SC measurement) was reached. The residual monomers and solvent were distilled off at 80 < 0 > C and 12 mbara.
밝은 황색빛 액체 중합체 총 291.29 g을 수득하였다. GPC (THF, PS-표준물, Mn = 7800 g/mol, PD = 1.27). 1H-NMR을 통한 분석에 따르면, 중합도는 78이었다.A total of 291.29 g of light yellow light liquid polymer was obtained. GPC (THF, PS-standard, Mn = 7800 g / mol, PD = 1.27). According to analysis by < 1 > H-NMR, the degree of polymerization was 78. [
실시예 A1: 폴리(n-BA-co-MPEG500A)Example A1: Synthesis of poly (n-BA-co-MPEG500A)
MPEG500을 사용한 에스테르교환Ester exchange using MPEG500
오버헤드 프로펠러 교반기, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼을 구비한 100 mL 플라스크 중에서, 실시예 B1에 따른 폴리(n-BA) 37.0 g 및 MPEG500 17.89 g (Mn = 500 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 10 mol%)을 첨가하고, 60 mbara 하에 60℃에서 60분 동안 탈기시킴으로써 건조시켰다. 플라스크 중 투명한 반응 매스를 135℃로 가열하였다. LiOtBu 93 mg의 2 부분을 130-135℃에서 4.5시간 동안 첨가하였다. 형성된 n-부탄올 (약 2.50 g)을 감압 (100 mbara) 하에 증류 제거하였다.In a 100 mL flask equipped with a distillation column equipped with an overhead propeller stirrer and dry ice acetone cooling, 37.0 g of poly (n-BA) according to Example B1 and 17.89 g of MPEG 500 (Mn = 500 g / mol, n-butyl ester ) Was added and dried by degassing at 60 < 0 > C for 60 minutes under 60 mbar. The clear reaction mass in the flask was heated to 135 占 폚. Two portions of LiOtBu 93 mg were added at 130-135 占 폚 for 4.5 hours. The formed n-butanol (about 2.50 g) was distilled off under reduced pressure (100 mbara).
폴리(n-BA-co-MPEG500A) A1 50.10 g을 갈색빛 점성 액체로서 수득하였다. Mn = 12900 g/mol, PD = 1.4. GPC 뿐만 아니라 1H-NMR을 통한 분석은 폴리글리콜의 거의 정량적인 전환을 나타내었다. SC = 98.0%.50.10 g of poly (n-BA-co-MPEG500A) Al were obtained as a brown viscous liquid. Mn = 12900 g / mol, PD = 1.4. Analysis by GPC as well as < 1 > H-NMR showed almost quantitative conversion of polyglycol. SC = 98.0%.
중합체 A1은 실온에서 물 중 1 중량% 용액으로서 유화되었다. NaCl 용액 중에서도 동일한 거동이 관찰되었으며, 50℃에서 중합체가 침전하는 점에서 차이가 있었다.Polymer A1 was emulsified as a 1 wt% solution in water at room temperature. The same behavior was observed in the NaCl solution and there was a difference in that the polymer precipitated at 50 ° C.
실시예 A2 내지 A6Examples A2 to A6
중합체 A1에 대해 기재된 바와 유사한 방식으로, 중합체 A2 내지 A6을 하기 표 1에 나타낸 몰비로 제조하였다.Polymers A2 to A6 were prepared in the molar ratios shown in Table 1 below in a similar manner as described for Polymer A1.
<표 1><Table 1>
생성된 중합체는 또한 다음 유기 용매들 중에서 투명한 5 중량% 용액을 형성하였다: 부틸 아세테이트, MPA, 메톡시프로판올, 부틸글리콜 및 크실렌.The resulting polymer also formed a transparent 5 wt% solution among the following organic solvents: butyl acetate, MPA, methoxypropanol, butyl glycol and xylene.
실시예 A7: 폴리(n-BA-co-MPEG500A-co-LuON70A)Example A7: Poly (n-BA-co-MPEG500A-co-LuON70A)
MPEG500 및 루텐솔® ON 70 (에톡실화 이소-C10 알콜)을 사용한 공-에스테르교환Ester exchange using MPEG500 and Rutensol® ON 70 (ethoxylated iso-C10 alcohol)
오버헤드 프로펠러 교반기, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼을 구비한 100 mL 플라스크 중에서, 실시예 B1에 따른 폴리(n-BA) 25.0 g, MPEG500 24.17 g (Mn = 500 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 20 mol%) 및 루텐솔® ON 70 11.26 g (Mn 약 466 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 10 mol%)을 첨가하고, 60 mbara 하에 60℃에서 60분 동안 탈기시킴으로써 건조시켰다. 플라스크 중 투명한 반응 매스를 135℃로 가열하였다. LiOtBu 108 mg의 4 부분을 130-135℃에서 6시간 동안 첨가하였다. 형성된 n-부탄올 (약 5.3 g)을 감압 (50 mbara) 하에 증류 제거하였다.In a 100 mL flask equipped with a distillation column equipped with an overhead propeller stirrer and a dry ice acetone cooling section, 25.0 g of poly (n-BA) according to Example B1, 24.17 g of MPEG 500 (Mn = 500 g / mol, 20 mol% based on the initial amount of n-butyl ester) and 11.26 g (Mn about 466 g / mol, 10 mol% based on the initial amount of n-butyl ester) of Rutensol® ON 70 were added and 60 Lt; 0 > C for 60 minutes. The clear reaction mass in the flask was heated to 135 占 폚. Four portions of LiOtBu 108 mg were added at 130-135 占 폚 for 6 hours. The formed n-butanol (about 5.3 g) was distilled off under reduced pressure (50 mbara).
폴리(n-BA-co-MPEG500A-co-LuON70A) A7 52.46 g을 갈색빛 점성 액체로서 수득하였다. Mn = 14330 g/mol, PD = 1.6. GPC 뿐만 아니라 1H-NMR을 통한 분석은 글리콜 에테르의 거의 정량적인 전환을 나타내었다. SC = 98.0%.52.46 g of poly (n-BA-co-MPEG500A-co-LuON70A) A7 was obtained as a brown viscous liquid. Mn = 14330 g / mol, PD = 1.6. Analysis by GPC as well as < 1 > H-NMR showed almost quantitative conversion of the glycol ether. SC = 98.0%.
중합체 A7은 실온에서 물 중 1 중량% 용액으로서 투명한 용액이었다. 1% NaCl 용액 중에서는 85℃의 LCST가 관찰되었다.Polymer A7 was a clear solution as a 1 wt% solution in water at room temperature. LCST at 85 ℃ was observed in 1% NaCl solution.
실시예 A8 내지 A11Examples A8 to A11
중합체 A7에 대해 기재된 바와 유사한 방식으로, 루텐솔® ON 70을 함유하는 중합체 A8 내지 A11을 하기 표 2에 나타낸 몰비로 제조하였다.In a similar manner as described for polymer A7, polymers A8 to A11 containing rutensol® ON 70 were prepared in the molar ratios shown in Table 2 below.
<표 2><Table 2>
실시예 B2: PCL1075 모노올의 합성.Example B2: Synthesis of PCL1075 monool.
오버헤드 프로펠러 교반기를 구비한 500 mL 플라스크 중에서, 세틸알콜 49.73 g (MW = 242.5 g/mol, 1 몰 당량) 및 엡실론-카프로락톤 171.3 g (MW = 114, 7.3 몰 당량)을 넣고, 건조 질소 분위기 하에 170℃로 가열하였다. 디부틸주석디라우레이트 촉매 2 방울 (약 100 mg)을 170℃에서 첨가한 다음, SC > 98 중량%에 도달할 때까지 내용물을 8시간 동안 교반하였다. 생성된 무색 폴리에스테르를 80℃로 냉각시키고, 유리 병에 채우고, 여기서 이를 왁스상 백색 고체 219 g로 고체화시켰다.49.73 g (MW = 242.5 g / mol, 1 molar equivalent) of cetyl alcohol and 171.3 g (MW = 114, 7.3 mol equivalent) of epsilon-caprolactone were placed in a 500 mL flask equipped with an overhead propeller stirrer, 0.0 > 170 C. < / RTI > Two drops of dibutyltin dilaurate catalyst (about 100 mg) were added at 170 占 폚 and then the contents were stirred for 8 hours until SC> 98% by weight. The resulting colorless polyester was cooled to 80 DEG C and filled in a vial where it was solidified to 219 g of a white solid as a wax.
1H-NMR은 폴리카프로락톤 모노올의 완전 전환을 나타내었으며, OH-가 52.02 mgKOH/g, SC 98.57%, 가드너(Gardner) 색 < 1인 것으로 측정되었다.The < 1 > H-NMR showed complete conversion of the polycaprolactone monool, with OH- being 52.02 mgKOH / g, SC 98.57% and Gardner color <1.
실시예 A12: 폴리(n-BA-co-MPEG500A-co-PCL1075A)Example A12: Poly (n-BA-co-MPEG500A-co-PCL1075A)
MPEG500 및 PCL1075를 사용한 공-에스테르교환Bond-ester exchange using MPEG500 and PCL1075
오버헤드 프로펠러 교반기, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼을 구비한 100 mL 플라스크 중에서, 실시예 B1에 따른 폴리(n-BA) 20.0 g, MPEG500 19.34 g (Mn = 500 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 20 mol%) 및 PCL1075 (실시예 B2) 20.11 g (Mn 약 1075 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 10 mol%)을 첨가하고, 60 mbara 하에 60℃에서 60분 동안 탈기시킴으로써 건조시켰다. 플라스크 중 투명한 반응 매스를 135℃로 가열하였다. LiOtBu 100 mg의 4 부분을 130-135℃에서 6시간 동안 첨가하였다. 형성된 n-부탄올 (약 4.3 g)을 감압 (50 mbara) 하에 증류 제거하였다.In a 100 mL flask equipped with a distillation column equipped with an overhead propeller stirrer and a dry ice acetone cooling section, 20.0 g of poly (n-BA) according to Example B1, 19.34 g of MPEG 500 (Mn = 500 g / mol, n-butyl ester (20 mol% based on the initial amount of n-butyl ester) and 20.11 g (Mn about 1075 g / mol, 10 mol% based on the initial amount of n-butyl ester) of PCL1075 And dried by degassing at 60 DEG C for 60 minutes. The clear reaction mass in the flask was heated to 135 占 폚. Four portions of LiOtBu 100 mg were added at 130-135 占 폚 for 6 hours. The formed n-butanol (about 4.3 g) was distilled off under reduced pressure (50 mbara).
폴리(n-BA-co-MPEG500A-co-PCL1075A) A12 52.31 g을 갈색빛 점성 액체로서 수득하였다. Mn = 22560 g/mol, PD = 1.69. GPC 뿐만 아니라 1H-NMR을 통한 분석은 MPEG500 및 폴리에스테롤의 전환율 > 95%를 나타내었다. SC = 98.3%52.31 g of poly (n-BA-co-MPEG500A-co-PCL1075A) A12 was obtained as a brown viscous liquid. Mn = 22560 g / mol, PD = 1.69. Analysis by GPC as well as < 1 > H-NMR showed a conversion of MPEG500 and polyestherol > 95%. SC = 98.3%
중합체 A12는 물 및 1% NaCl 용액 둘 다 중에서 에멀젼을 형성하였으며, 1% NaCl 용액 중에서 이는 60℃에서 침전하였다.Polymer A12 formed an emulsion in both water and 1% NaCl solution, which was precipitated at 60 C in 1% NaCl solution.
실시예 A13: 폴리(n-BA-co-MPEG500A-co-PCL1075A)Example A13: Poly (n-BA-co-MPEG500A-co-PCL1075A)
MPEG500 및 PCL1075를 사용한 연속적 에스테르교환Continuous ester exchange using MPEG500 and PCL1075
오버헤드 프로펠러 교반기, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼을 구비한 100 mL 플라스크 중에서, 실시예 B1에 따른 폴리(n-BA) 20.0 g 및 MPEG500 19.34 g (Mn = 500 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 20 mol%)을 첨가하고, 60 mbara 하에 60℃에서 60분 동안 탈기시킴으로써 건조시켰다. 플라스크 중 투명한 반응 매스를 135℃로 가열하였다. LiOtBu 93 mg의 3 부분을 130-135℃에서 5.5시간 동안 첨가하였다. 전환의 완결 (n-부탄올 형성 없음) 후에, 반응 매스에 PCL1075 (실시예 B2) 20.11 g (Mn 약 1075 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 10 mol%)를 첨가하고, LiOtBu 93 mg의 3 부분을 첨가하여 135℃에서 추가 4시간 동안 계속 에스테르교환하였다. 형성된 n-부탄올의 총량 (약 4.3 g)을 감압 (50 mbara) 하에 증류 제거하였다.20.0 g of poly (n-BA) according to Example B1 and 19.34 g of MPEG 500 (Mn = 500 g / mol, n-butyl ester < RTI ID = ) Was added and dried by degassing at 60 DEG C for 60 minutes under 60 mbar. The clear reaction mass in the flask was heated to 135 占 폚. Three portions of LiOtBu 93 mg were added at 130-135 占 폚 for 5.5 hours. After the completion of the conversion (no n-butanol formation), 20.11 g (Mn about 1075 g / mol, 10 mol% based on the initial amount of n-butyl ester) of PCL1075 (Example B2) Three portions of LiOtBu 93 mg were added and the mixture was continuously transesterified at 135 < 0 > C for an additional 4 hours. The total amount of n-butanol formed (about 4.3 g) was distilled off under reduced pressure (50 mbara).
폴리(n-BA-co-MPEG500A-co-PCL1075A) A13 51.39 g을 갈색빛 점성 액체로서 수득하였다. Mn = 22690 g/mol, PD = 1.78. GPC 뿐만 아니라 1H-NMR을 통한 분석은 MPEG500 및 폴리에스테롤의 전환율 > 95%를 나타내었다. SC = 98.4%.51.39 g of poly (n-BA-co-MPEG500A-co-PCL1075A) A13 was obtained as a brown viscous liquid. Mn = 22690 g / mol, PD = 1.78. Analysis by GPC as well as < 1 > H-NMR showed a conversion of MPEG500 and polyestherol > 95%. SC = 98.4%.
중합체 A13은 물 중에서 RT에서 투명한 에멀젼을 형성하고 65℃에서 혼탁해졌으며, 1% NaCl 용액 중에서 RT에서 에멀젼을 형성하고 60℃에서 중합체가 침전하였다.Polymer A13 formed a clear emulsion at RT in water and turbid at 65 ° C, forming an emulsion at RT in 1% NaCl solution and precipitating the polymer at 60 ° C.
실시예 A14 내지 A15Examples A14 to A15
중합체 A13에 대해 기재된 바와 유사한 방식으로, PCL1075를 함유하는 중합체 A14 내지 A15 및 A25를 하기 표 3에 나타낸 몰비로 제조하였다.Polymers A14 to A15 and A25 containing PCL1075 were prepared in the molar ratios shown in Table 3 below, in a similar manner as described for Polymer A13.
<표 3><Table 3>
실시예 A18: 폴리(n-BA-co-MPEG500A-co-HEMOA)Example A18: Poly (n-BA-co-MPEG500A-co-HEMOA)
MPEG500과 HEMO를 사용한 공-에스테르교환Bond-ester exchange using MPEG500 and HEMO
오버헤드 프로펠러 교반기, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼을 구비한 100 mL 플라스크 중에서, 실시예 B1에 따른 폴리(n-BA) 27.0 g, MPEG500 26.11 g (Mn = 500 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 20 mol%) 및 HEMO 3.42 g (MW = 131 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 10 mol%)을 첨가하고, 80 mbara 하에 80℃에서 60분 동안 탈기시킴으로써 건조시켰다. 플라스크 중 투명한 반응 매스를 135℃로 가열하였다. LiOtBu 98 mg의 4 부분을 130-135℃에서 6시간 동안 첨가하였다. 형성된 n-부탄올 (약 5.8 g)을 감압 (45 mbara) 하에 증류 제거하였다.In a 100 mL flask equipped with a distillation column equipped with an overhead propeller stirrer and dry ice acetone cooling, 27.0 g of poly (n-BA) according to Example B1 and 26.11 g of MPEG 500 (Mn = 500 g / mol, n-butyl ester ) And HEMO (3.42 g, MW = 131 g / mol, 10 mol% based on the initial amount of n-butyl ester) were added and heated to 80 <Lt; / RTI > The clear reaction mass in the flask was heated to 135 占 폚. Four portions of LiOtBu 98 mg were added at 130-135 占 폚 for 6 hours. The formed n-butanol (about 5.8 g) was distilled off under reduced pressure (45 mbara).
폴리(n-BA-co-MPEG500A-co-HEMOA) A18 49.0 g을 갈색빛 점성 액체로서 수득하였다. Mn = 11430 g/mol, PD = 1.76. GPC 뿐만 아니라 1H-NMR을 통한 분석은 MPEG500의 전환율 > 95%를 나타내었다. SC = 98.2%.49.0 g of poly (n-BA-co-MPEG500A-co-HEMOA) A18 was obtained as a brown viscous liquid. Mn = 11430 g / mol, PD = 1.76. Analysis by GPC as well as < 1 > H-NMR showed a conversion of MPEG500 of > 95%. SC = 98.2%.
중합체 A18은 순수한 물 중에서 85℃ 미만의 LCST를 나타내지 않았으나, 1% NaCl 중에서 60℃의 LCST를 나타내었다.Polymer A18 did not show an LCST below 85 ° C in pure water, but showed an LCST of 60 ° C in 1% NaCl.
실시예 A19 내지 A24Examples A19 to A24
중합체 A18에 대해 기재된 바와 유사한 방식으로, HEMO를 함유하는 중합체 A19 내지 A24를 하기 표 4에 나타낸 몰비로 제조하였다.In a similar manner as described for polymer A18, polymers A19 to A24 containing HEMO were prepared in the molar ratios shown in Table 4 below.
<표 4><Table 4>
실시예 A26: 폴리(n-BA-co-솔케탈A)Example A26: Synthesis of Poly (n-BA-co-Solketal A)
솔케탈 ((+/-)-2,2-디메틸-4-히드록시메틸-1,3-디옥솔란)을 사용한 에스테르교환((+/-) - 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane)
오버헤드 프로펠러 교반기, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼을 구비한 100 mL 플라스크 중에서, 실시예 B1에 따른 폴리(n-BA) 40.0 g 및 솔케탈 25.56 g (Mn = 132 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 50 mol%)을 첨가하고, 80 mbara 하에 80℃에서 60분 동안 탈기시킴으로써 건조시켰다. 플라스크 중 투명한 반응 매스를 135℃로 가열하였다. LiOtBu 100 mg의 5 부분을 130-135℃에서 13시간 동안 첨가하였다. 형성된 n-부탄올 (약 14.3 g)을 감압 (60 mbara) 하에 증류 제거하였다.In a 100 mL flask equipped with a distillation column equipped with an overhead propeller stirrer and dry ice acetone cooling, 40.0 g of poly (n-BA) according to Example B1 and 25.56 g (Mn = 132 g / mol, 50 mol% based on the initial amount of ester) was added and dried by degassing at 80 DEG C for 60 minutes under 80 mbara. The clear reaction mass in the flask was heated to 135 占 폚. Five portions of LiOtBu 100 mg were added at 130-135 占 폚 for 13 hours. The formed n-butanol (about 14.3 g) was distilled off under reduced pressure (60 mbara).
폴리(n-BA-co-솔케탈A) A26 43.1 g을 갈색빛 점성 액체로서 수득하였다. Mn = 10470 g/mol, PD = 1.57. SC는 96.9%로 측정되었다. GPC 뿐만 아니라 1H-NMR을 통한 분석은 디올의 비보호 없이 솔케탈의 완전 전환을 나타내었다.43.1 g of poly (n-BA-co-solketal A) A26 were obtained as a brown viscous liquid. Mn = 10470 g / mol, PD = 1.57. SC was measured at 96.9%. Analysis by GPC as well as < 1 > H-NMR showed complete conversion of the sorbitan without protection of the diol.
중합체 A26은 순수한 물 중에서나 1% NaCl 용액 중에서도 가용성을 나타내지 않았다.Polymer A26 did not show solubility in pure water or in 1% NaCl solution.
실시예 A27 내지 A31Examples A27 to A31
중합체 A26에 대해 기재된 바와 유사한 방식으로, HEMO를 함유하는 중합체 A27 내지 A31을 하기 표 5에 나타낸 몰비로 제조하였다.In a similar manner as described for polymer A26, polymers A27 through A31 containing HEMO were prepared in the molar ratios shown in Table 5 below.
<표 5><Table 5>
실시예 A32: TFAA를 사용한 폴리(n-BA-co-MPEG500A-co-솔케탈A)의 폴리(n-BA-co-MPEG500A-co-글리세릴A)로의 탈보호Example A32 Deprotection of poly (n-BA-co-MPEG500A-co-Solketal A) with poly (n-BA-co-MPEG500A-co-glyceryl A) using TFAA
오버헤드 프로펠러 교반기를 구비한 100 mL 플라스크 중에서, 실시예 A30에 따른 중합체 5.5 g을 THF 11.0 g, H2O 11.0 g 및 MeOH 5.0 g 중에 용해시켰다. 실온에서 트리플루오로아세트산 무수물 (MW = 230) 1.1 g을 첨가한 다음, 내용물을 80℃로 가열하고 18시간 동안 교반하였다. 생성된 갈색빛 용액을 NMR에 의해 분석하여 모든 아세탈 기가 없어진 것을 확인하였다. 중합체 용액을 SC 94.5%까지 감압 (100 mbara) 하에 농축시켜 점성 갈색빛 액체 4.5 g을 수득하였다. Mn = 10770 g/mol, PD = 1.50. 1H-NMR은 솔케탈 단위의 완전 탈보호를 나타내었다.In a 100 mL flask equipped with an overhead propeller stirrer, 5.5 g of the polymer according to Example A30 was dissolved in 11.0 g of THF, 11.0 g of H 2 O and 5.0 g of MeOH. At room temperature, 1.1 g of trifluoroacetic anhydride (MW = 230) was added and the contents were heated to 80 DEG C and stirred for 18 hours. The resulting brown light solution was analyzed by NMR to confirm that all of the acetal groups had disappeared. The polymer solution was concentrated to SC 94.5% under reduced pressure (100 mbara) to give 4.5 g of a viscous brown liquid. Mn = 10770 g / mol, PD = 1.50. ≪ 1 > H-NMR indicated complete deprotection of the solketal unit.
중합체 A32는 순수한 물 중에서 55℃ 및 1% NaCl 용액 중에서 50℃의 LCST를 나타내었다.Polymer A32 exhibited an LCST of 55 [deg.] C in pure water and 50 [deg.] C in 1% NaCl solution.
실시예 A35: 도웩스를 사용한 폴리(n-BA-co-MPEG500A-co-솔케탈A)의 폴리(n-BA-co-MPEG500A-co-글리세릴A)로의 탈보호Example A35: Deprotection of poly (n-BA-co-MPEG500A-co-Solketal A) with poly (n-BA-co-MPEG500A-co-glyceryl A) using Dowex
오버헤드 프로펠러 교반기를 구비한 100 mL 플라스크 중에서, 실시예 A29에 따른 중합체 5.55 g을 THF 11.1 g, H2O 11.1 g 및 EtOH 5.0 g 중에 용해시켰다. 실온에서 도웩스 50WX8 (산성 수지) 1.1 g을 첨가한 다음, 내용물을 80℃로 가열하고 18시간 동안 교반하였다. 생성된 갈색빛 용액에 도웩스 50WX8 추가 부분 (1.1 g)에 이어서 H2O 1.0 g을 첨가하였다. 80℃에서 추가 18시간 동안 교반한 후에, 중합체 용액을 여과하고, 감압 (100 mbara) 하에 SC 98.8%까지 농축시켜 점성 갈색빛 액체 4.3 g을 수득하였다. Mn = 13200 g/mol, PD = 1.62. 1H-NMR은 솔케탈 단위의 완전 탈보호를 나타내었다.In a 100 mL flask equipped with an overhead propeller stirrer, 5.55 g of the polymer according to Example A29 was dissolved in 11.1 g of THF, 11.1 g of H 2 O and 5.0 g of EtOH. At room temperature, 1.1 g of Dowex 50WX8 (acid resin) was added and the contents were heated to 80 DEG C and stirred for 18 hours. To the resulting light brown solution was then also in Wexford 50WX8 further portion (1.1 g) was added to H 2 O 1.0 g. After stirring at 80 ° C for an additional 18 hours, the polymer solution was filtered and concentrated to a SC 98.8% under reduced pressure (100 mbara) to give 4.3 g of a viscous brown liquid. Mn = 13200 g / mol, PD = 1.62. ≪ 1 > H-NMR indicated complete deprotection of the solketal unit.
중합체 A35는 순수한 물 및 1% NaCl 용액 둘 다 중에서 에멀젼이 되었다.Polymer A35 emulsified in both pure water and 1% NaCl solution.
실시예 A37: TFAA 및 PTSA의 조합물을 사용한 폴리(n-BA-co-MPEG500A-co-솔케탈A)의 폴리(n-BA-co-MPEG500A-co-글리세릴A)로의 탈보호Example A37: Deprotection of poly (n-BA-co-MPEG500A-co-Solketal A) with poly (n-BA-co-MPEG500A-co-glyceryl A) using a combination of TFAA and PTSA
오버헤드 프로펠러 교반기를 구비한 100 mL 플라스크 중에서, 실시예 A31에 따른 중합체 12.5 g을 THF 6.5 g, H2O 0.65 g 및 EtOH 6.0 g 중에 용해시켰다. 실온에서 트리플루오로아세트산 무수물 (MW = 230) 0.185 g 및 파라-톨루엔술폰산 1수화물 (MW = 190) 0.75 g을 첨가한 다음, 내용물을 80℃로 가열하고 18시간 동안 교반하였다. PTSA 및 TFAA 추가 부분 (동일한 양) 및 물 2.0 g을 첨가하고, 80℃에서 추가 18시간 동안 교반하였다. 최종적으로, 중합체 용액을 감압 (100 mbara) 하에 SC 96.5%까지 농축시켜 점성 갈색빛 액체 10.9 g을 수득하였다. Mn = 8670 g/mol, PD = 1.49. 1H-NMR은 솔케탈 단위의 완전 탈보호를 나타내었다.In a 100 mL flask equipped with an overhead propeller stirrer, 12.5 g of the polymer according to Example A31 was dissolved in 6.5 g of THF, 0.65 g of H 2 O and 6.0 g of EtOH. At room temperature, 0.185 g of trifluoroacetic anhydride (MW = 230) and 0.75 g of para-toluenesulfonic acid monohydrate (MW = 190) were added and the contents were heated to 80 DEG C and stirred for 18 hours. Additional portions of PTSA and TFAA (the same amount) and 2.0 g of water were added and stirred for an additional 18 hours at 80 < 0 > C. Finally, the polymer solution was concentrated to 96.5% SC under reduced pressure (100 mbara) to give 10.9 g of a viscous brown liquid. Mn = 8670 g / mol, PD = 1.49. ≪ 1 > H-NMR indicated complete deprotection of the solketal unit.
생성된 중합체는 순수한 물 중에서 55℃ 및 1%NaCl 용액 중에서 50℃의 LCST를 나타내었다.The resulting polymer exhibited an LCST of 55 DEG C in pure water and 50 DEG C in 1% NaCl solution.
실시예 A33 내지 A38Examples A33 to A38
중합체 A32에 대해 기재된 바와 유사한 방식으로, 중합체 A33 내지 A38을 하기 표 6에서의 그들의 전구체로부터 제조하였다.Polymers A33 through A38 were prepared from their precursors in the following Table 6, in a similar manner as described for Polymer A32.
<표 6><Table 6>
실시예 A34: 폴리(n-BA-co-HEMO[H+]A-co-글리세릴A)의 제조Example A34: Preparation of poly (n-BA-co-HEMO [H + ] A-co-glyceryl A)
오버헤드 프로펠러 교반기를 구비한 100 mL 플라스크 중에서, 실시예 A28에 따른 중합체 5.55 g을 THF 11.1 g, H2O 11.1 g 및 EtOH 5.0 g 중에 용해시켰다. 실온에서 TFAA (MW = 230) 1.1 g을 첨가한 다음, 내용물을 80℃로 가열하고 18시간 동안 교반하였다. 중합체 용액을 감압 (100 mbara) 하에 SC 95.5%까지 농축시켜 고점성 갈색빛 액체 5.1 g을 수득하였다. Mn = 5340 g/mol, PD = 2.16. 1H-NMR은 솔케탈 단위의 완전 탈보호를 나타내었으며, HEMO 기들 중 일부 (25%)는 트리플루오로아세테이트로서 수득되었다.In a 100 mL flask equipped with an overhead propeller stirrer, 5.55 g of the polymer according to Example A28 was dissolved in 11.1 g of THF, 11.1 g of H 2 O and 5.0 g of EtOH. After addition of 1.1 g of TFAA (MW = 230) at room temperature, the contents were heated to 80 DEG C and stirred for 18 hours. The polymer solution was concentrated to 95.5% SC under reduced pressure (100 mbara) to give 5.1 g of a viscous brown liquid. Mn = 5340 g / mol, PD = 2.16. ≪ 1 > H-NMR indicated complete deprotection of the solketal unit and some (25%) of the HEMO groups were obtained as trifluoroacetate.
중합체 A34는 순수한 물 및 1% NaCl 용액 둘 다 중에서 85℃ 초과의 LCST를 가지며, 출발 중합체 A28은 이들 두 매질 중에서 가용성을 나타내지 않았다.Polymer A34 had an LCST of greater than 85 캜 in both pure water and 1% NaCl solution and starting polymer A28 did not show solubility in these two media.
실시예 A39: 폴리(n-BA-co-HEMOquat[+]A-co-글리세릴A)의 제조Example A39: Preparation of poly (n-BA-co-HEMOquat [ + ] A-co-glyceryl A)
오버헤드 프로펠러 교반기를 구비한 100 mL 플라스크 중에서, 실시예 A18에 따른 중합체 5.0 g을 H2O 10.0 g 중에 용해시키고, 에틸브로마이드 1.42 g (MW 109, HEMO 단위에 대해 50 mol%)을 실온에서 첨가하였다. 투명한 용액을 RT에서 6시간 동안 교반하고, 후속적으로 추가 작업 없이 유리 병에 채웠다 (수득량 15.97 g). 고체 함량은 28.5%이다. THF 중에서의 4급 중합체의 불용성으로 인해, GPC 분석은 수행할 수 없었다.In a 100 mL flask equipped with an overhead propeller stirrer, 5.0 g of the polymer according to Example A18 was dissolved in 10.0 g of H 2 O and 1.42 g of ethyl bromide (MW 109, 50 mol% for HEMO units) was added at room temperature Respectively. The clear solution was stirred at RT for 6 h and subsequently charged to the vial without further work (yield 15.97 g). The solid content is 28.5%. Due to the insolubility of the quaternary polymer in THF, GPC analysis could not be performed.
중합체 A39는 순수한 물 및 1% NaCl 용액 둘 다 중에서 85℃ 초과의 LCST를 가졌다.Polymer A39 had an LCST of greater than 85 [deg.] C in both pure water and 1% NaCl solution.
실시예 A40Example A40
중합체 A39에 대해 기재된 바와 유사한 방식으로, 중합체 A40을 하기 표 7에 나타낸 바와 같이 실시예 A21로부터 제조하였다.In a similar manner as described for Polymer A39, Polymer A40 was prepared from Example A21 as shown in Table 7 below.
<표 7><Table 7>
실시예 A51: 폴리(n-BA-co-MPEG500A-co-LuN400A)Example A51: Poly (n-BA-co-MPEG500A-co-LuN400A)
MPEG500 및 루프라겐® N 400을 사용한 공-에스테르교환Ester exchange using MPEG500 and Loop Lagen® N 400
오버헤드 프로펠러 교반기, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼을 구비한 100 mL 플라스크 중에서, 실시예 B1에 따른 폴리(n-BA) 27.0 g, MPEG500 26.11 g (Mn = 500 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 20 mol%) 및 루프라겐® N 400 3.82 g (Mn 146 g/mol, n-부틸에스테르의 최초 양을 기준으로 하여 10 mol%)을 첨가하고, 100 mbara 하에 70℃에서 60분 동안 탈기시킴으로써 건조시켰다. 플라스크 중 투명한 반응 매스를 135℃로 가열하였다. LiOtBu 100 mg의 4 부분을 130-135℃에서 6시간 동안 첨가하였다. 형성된 n-부탄올 (약 5.8 g)을 감압 (80 mbara) 하에 증류 제거하였다.In a 100 mL flask equipped with a distillation column equipped with an overhead propeller stirrer and dry ice acetone cooling, 27.0 g of poly (n-BA) according to Example B1 and 26.11 g of MPEG 500 (Mn = 500 g / mol, n-butyl ester ) And 3.82 g (Mn 146 g / mol, 10 mol% based on the initial amount of n-butyl ester) of LUORAGEN® N 400 were added and heated to 70 ° C Lt; / RTI > for 60 minutes. The clear reaction mass in the flask was heated to 135 占 폚. Four portions of LiOtBu 100 mg were added at 130-135 占 폚 for 6 hours. The formed n-butanol (about 5.8 g) was distilled off under reduced pressure (80 mbara).
폴리(n-BA-co-MPEG500A-co-LuN400A) 48.57 g을 갈색빛 점성 액체로서 수득하였다. Mn = 16760 g/mol, PD = 1.88. GPC 뿐만 아니라 1H-NMR을 통한 분석은 MPEG-OH 및 아미노알콜의 전환율 > 95%를 나타내었다. SC = 97.8%.48.57 g of poly (n-BA-co-MPEG500A-co-LuN400A) was obtained as a brown viscous liquid. Mn = 16760 g / mol, PD = 1.88. Analysis by 1 H-NMR as well as by GPC showed a conversion of MPEG-OH and amino alcohol of > 95%. SC = 97.8%.
실시예 A52 내지 A54Examples A52 to A54
중합체 A51에 대해 기재된 바와 유사한 방식으로, 루프라겐 N 400을 함유하는 중합체 A52 내지 A54를 하기 표 8에 나타낸 몰비로 제조하였다.In a similar manner as described for polymer A51, Polymers A52 through A54 containing loophen N 400 were prepared in the molar ratios shown in Table 8 below.
<표 8><Table 8>
실시예 B3: 선형 블록 공중합체 폴리(nBA-b-4VP)의 합성Example B3: Synthesis of linear block copolymer poly (nBA-b-4VP)
자기 교반 막대, 냉각기 및 온도계를 갖춘 3구 500 mL 둥근 바닥 플라스크 중에서, nBA 74 단위의 중합도 (1H NMR에 의함)를 갖는 실시예 B1에 따른 폴리(n-BA) 214.18g, 4-비닐피리딘 (4VP, MW = 105 g/mol) 70.90 g 및 MPA 79.70 g을 첨가하고, N2/진공으로 3회 탈기시키고, N2 하에 125℃에서 8시간 동안 중합시켰다. 잔류 단량체 및 용매를 SC > 98%에 도달할 때까지 80℃ 및 12 mbara에서 증류 제거하고, 후속적으로 MPA 60.0 g으로 SC 80%까지 희석하여 B3 (302.2 g)을 점성 황색빛-오렌지색 액체로서 수득하였다. 용매-무함유 중합체의 소량의 샘플을 GPC에 의해 분석하였다 (THF, PS-표준물, Mn = 8600 g/mol, PD = 1.24). 블록 길이는 1H NMR에 의해 nBA 73 단위 및 4VP 15 단위로 측정되었다.214.18 g of poly (n-BA) according to Example B1 having a degree of polymerization of nBA 74 units (by < 1 > H NMR) in a three-necked 500 mL round bottom flask equipped with magnetic stirrer, condenser and thermometer, 4-vinylpyridine 4VP, MW = 105 g / mol) and 79.70 g of MPA were added, degassed N 2 / vacuum three times and polymerized at 125 ° C for 8 hours under N 2 . The residual monomer and solvent were distilled off at 80 DEG C and 12 mbara until SC> 98% was reached, and subsequently B3 (302.2 g) was diluted to 60.0 g of MP with SC 80% to yield a viscous yellow light-orange liquid . A small sample of the solvent-free polymer was analyzed by GPC (THF, PS-standard, Mn = 8600 g / mol, PD = 1.24). The block length was measured by nHBA 73 units and 4VP 15 units by < 1 > H NMR.
실시예 C1: 폴리([n-BA-co-MPEG500A]-b-4VP)Example C1: Poly ([n-BA-co-MPEG500A] -b-4VP)
자기 교반 막대, 드라이아이스 아세톤 냉각부를 갖춘 증류 칼럼를 구비한 350 mL 플라스크 중에서, 실시예 B3에 따라 제조된 MPA 중 폴리(n-BA-b-4VP) (80% 고형분) 150.0 g을 MPEG 500 80.0 g과 혼합하였다. 90℃에서, 용매를 감압 하에 증류 제거하고, 진공 (20 mbara) 하에 130℃로 1시간 동안 추가 가열하여 미량의 습기를 제거하였다. LiOtBu 800 mg의 3 부분을 115-130℃에서 6시간 동안 첨가하였다. 형성된 n-부탄올 (약 11,8 g)을 감압 (20 mbara) 하에 증류 제거하였다. 최종 생성물 (188.2 g, 갈색빛 액체)을 H2O로 50 중량%까지 희석하였다. GPC 뿐만 아니라 1H-NMR을 통한 분석은 MPEG500의 완전 전환을 나타내었다. GPC: Mn = 9120 g/mol, PD = 1.87.150.0 g of poly (n-BA-b-4VP) (80% solids) in MPA prepared according to Example B3 in a 350 mL flask equipped with a magnetic stir bar and a distillation column equipped with a dry ice acetone cooling was charged with MPEG 500 80.0 g ≪ / RTI > At 90 占 폚, the solvent was distilled off under reduced pressure and further heated for 1 hour at 130 占 폚 under vacuum (20 mbara) to remove trace moisture. Three portions of LiOtBu 800 mg were added at 115-130 [deg.] C for 6 hours. The formed n-butanol (about 11.8 g) was distilled off under reduced pressure (20 mbara). The final product (188.2 g, brownish liquid) was diluted with H 2 O to 50% by weight. Analysis by GPC as well as 1 H-NMR showed complete conversion of MPEG 500. GPC: Mn = 9120 g / mol, PD = 1.87.
중합체 C1은 실온에서 물 중에서 투명한 용액 (10 중량%)이었으며, 65℃ 초과의 LCST를 나타내었다.Polymer C1 was a clear solution (10 wt%) in water at room temperature and exhibited an LCST of greater than 65 ° C.
실시예 C2 내지 C4Examples C2 to C4
중합체 C1에 대해 기재된 바와 유사한 방식으로, MPEG 500을 함유하는 블록 중합체 C2 내지 C4를 하기 표 9에 나타낸 몰비로 제조하였다.In a manner similar to that described for polymer C1, block polymers C2 to C4 containing MPEG 500 were prepared in the molar ratios shown in Table 9 below.
<표 9><Table 9>
B) 적용 결과B) Application result
세제에서의 본 발명에 따른 빗살형 공중합체의 방오 효과의 시험Test of the antifouling effect of the comb type copolymer according to the present invention in a detergent
5 g의 백색 폴리에스테르 직물 (WfK 30A)의 포를 세척액 100 ml 중에서 처리하였다. 세척액은 16° 독일 경도의 물, 4.7 g/l 농도의 표준 세척제 (AATCC 2003 표준 액체 규격 세제 WOB 오더 넘버(AATCC 2003 Standard Liquid Reference Detergent WOB Order No.) 08804) 및 임의로 본 발명의 활성 중합체 중 1종 0.094 g/L를 함유하였다. 처리는 리니테스트(LINITEST) 장치의 스틸 비커 중에서 40℃에서 30분 동안 수행하였다. 그 후에 텍스타일을 흐르는 수돗물 하에 세정하고, 회전 건조시키고, 45℃에서 30분 동안 건조시켰다. 동일한 포를 사용하지만 새로운 세척액을 사용하여 상기 절차를 2회 반복하였다 (이에 따라 총 3회의 예비-세척 사이클).5 g of a white polyester fabric (WfK 30A) was treated in 100 ml of wash solution. The washings consisted of 16 deg. German hardness water, a standard detergent (AATCC 2003 Standard Liquid Reference Detergent Wob Order No. 08804) at a concentration of 4.7 g / l and optionally 1 < RTI ID = 0.0 > Species 0.094 g / L. The treatment was carried out in a steel beaker of a LINITEST apparatus at 40 DEG C for 30 minutes. The textile was then rinsed under running tap water, spin-dried and dried at 45 DEG C for 30 minutes. The procedure was repeated twice using the same wash but with fresh wash solution (thus a total of 3 pre-wash cycles).
후속적으로 포를 실온에서 2시간 동안 순응되게 한 다음, 피펫에 의해 도포하여 50 μL의 더러운 모터 오일로 각각 오염시켰다. 얼룩을 실온에서 밤새 건조되게 하였다. 다음날에 얼룩의 CIE 명도 Y를 그레택(GRETAG) SPM100 재방출 분광계로 측정하였다. 후속적으로 예비-세척 사이클에 대해 상기 기재된 바와 동일한 조건 하에 동일한 세척액 조성물 중에서 각각 오염된 포를 리니테스트 비커 중에서 100 ml 세척액으로 세척하였다. 후속적으로 포를 45℃에서 30분 동안 건조시키고, 실온에서 2시간 동안 순응되게 한 후에, 얼룩의 명도 Y를 측정하였다.Subsequently, the pellets were allowed to acclimate for 2 hours at room temperature and then applied by pipette to contaminate each with 50 μL of dirty motor oil. The stain was allowed to dry overnight at room temperature. The next day, the CIE brightness Y of the stain was measured with a GRETAG SPM100 re-emission spectrometer. Subsequently, each of the contaminated pellets in the same wash liquor composition under the same conditions as described above for the pre-wash cycle was washed with 100 ml of wash solution in a beak test. Subsequently, after the blanket was dried at 45 캜 for 30 minutes and allowed to acclimate for 2 hours at room temperature, the brightness Y of the stain was measured.
세척 전후의 더러운 모터 오일 얼룩의 명도 Y의 차이를 DY로 표시하여, 세척액의 세척 성능의 측정값을 제공한다.The difference in lightness Y of the dirty motor oil stain before and after cleaning is denoted by DY to provide a measure of the cleaning performance of the cleaning fluid.
유형 A, B 또는 C의 여러 중합체들에 대한 DY 값을 하기 표 B1에 나타내었다.The DY values for the various polymers of type A, B or C are shown in Table B1 below.
<표 B1><Table B1>
본 발명의 공중합체에 대해 더러운 모터 오일 얼룩의 명도 개선도 DY의 현저한 증가가 관찰되었다.Significant increase in brightness improvement degree DY of dirty motor oil stains was observed for the copolymer of the present invention.
세제에서의 본 발명의 공중합체의 재부착방지 효과의 시험.Testing of anti-reattachment effects of the inventive copolymers in detergents.
16˚ 독일 경도의 물, 4.7 g/l 농도의 표준 세척제 (AATCC 2003 표준 액체 규격 세제 WOB 오더 넘버 08804), 0.03 g/L 농도의 그을음 (코락스(Corax) N765) 및 임의로 본 발명의 활성 중합체 중 1종 0.075 g/L를 함유하는 세척액을 제조하였다. 세척액을 먼저 자기 교반기를 사용하여 10분 동안 교반하고, 후속적으로 초음파조 중에서 10분 동안 처리하고, 최종적으로 자기 교반기를 사용하여 10분 동안 다시 교반하였다. 교반 하에 100 g의 세척액을 리니테스트 장치의 비커에 채우고, 5 g의 백색 면 직물 (WfK 13AK)의 포를 첨가하였다. 비커를 밀폐하고, 백색 면을 세척액 중에서 40℃에서 30분 동안 처리하였다. 텍스타일을 흐르는 수돗물 하에 세정한 후에, 회전 건조시키고, 45℃에서 30분 동안 건조시켰다. 동일한 면포를 사용하지만 새로운 세척액 및 새로운 그을음을 사용하여 상기 절차를 2회 반복하였다 (이에 따라 총 3회의 세척 사이클). 후속적으로, 포의 CIE 명도 Y를 데이터-컬러 스펙트럼 플래쉬(DATA-COLOR Spectra Flash) SF500 재방출 분광계로 측정하였다.(Corat N765) at a concentration of 0.03 g / L, and optionally an active polymer of the present invention (< RTI ID = 0.0 > 0.075 g / L was prepared. The washings were first stirred for 10 minutes using a magnetic stirrer, subsequently treated for 10 minutes in an ultrasonic bath and finally stirred again for 10 minutes using a magnetic stirrer. 100 g of wash solution under agitation was filled into the beaker of the Lini test apparatus and 5 g of a white cotton fabric (WfK 13AK) was added. The beaker was sealed, and the white surface was treated in the wash solution at 40 占 폚 for 30 minutes. The textile was washed under running tap water, then spin-dried and dried at 45 DEG C for 30 minutes. The procedure was repeated twice using the same cotton but with a new wash and new soot (thus a total of three wash cycles). Subsequently, the CIE brightness Y of the gun was measured with a DATA-COLOR Spectra Flash SF500 re-emission spectrometer.
3회의 세척 사이클 후 면포의 명도 Y는 본 발명의 공중합체를 함유하는 세척액의 재부착방지 성능에 대한 측정값이다. 그을음을 첨가하지 않은 것을 제외하고는 동일한 방식으로 포를 세척한 경우에, 포는 약 89의 명도 Y를 가졌다.The lightness Y of the cotton yarn after three washing cycles is a measure of the anti-redeposition performance of the washing liquid containing the copolymer of the present invention. When the can was washed in the same manner except that no soot was added, the gun had a brightness Y of about 89.
유형 A, B 또는 C의 여러 중합체들에 대한 Y 값을 하기 표 B2에 나타내었다.The Y values for the various polymers of type A, B or C are shown in Table B2 below.
<표 B2><Table B2>
본 발명의 중합체를 함유하는 중합체에 대해 3회의 세척 사이클 후 면 직물의 명도 Y의 현저한 증가가 관찰되었다. 많은 경우에, 소듐 카르복시메틸셀룰로스, 현재 기술 현황에 비해 매우 현저한 개선이 관찰되었다.A significant increase in the lightness Y of the cotton fabric was observed after three washing cycles for the polymer containing the polymer of the present invention. In many cases, sodium carboxymethylcellulose, a very significant improvement compared to the state of the art is observed.
Claims (5)
a) n-부틸아크릴레이트의 제어 자유 라디칼 중합에 의해 제조되고; 제2 단계에서
b) 1급 또는 2급 알콜을 사용한 중합체 유사 에스테르교환 반응으로 개질되어
빗살형 또는 블록 공중합체가 형성되며,
여기서 단계 b)의 1급 또는 2급 알콜은
폴리에틸렌 글리콜 모노메틸에테르,
N,N,N'-트리메틸아미노에틸에탄올아민,
N-히드록시에틸모르폴린, 또는
750 내지 2500 g/mol의 분자량을 갖는 폴리카프로락톤 α-세틸옥시,-ω-히드록시인
작용제.An agent as an antifouling agent and an antifouling agent in an aqueous washing process, which comprises at least one comb or block copolymer, wherein the comb or block copolymer comprises
a) prepared by controlled free radical polymerization of n-butyl acrylate; In the second step
b) modified by polymeric transesterification using primary or secondary alcohols
A comb-like or block copolymer is formed,
Wherein the primary or secondary alcohol of step b)
Polyethylene glycol monomethyl ether,
N, N, N'-trimethylaminoethylethanolamine,
N-hydroxyethylmorpholine, or
Polycaprolactone having a molecular weight of 750 to 2500 g / mol? -Cetyloxy,? -Hydroxyin
agent.
a) n-부틸아크릴레이트의 제어 자유 라디칼 중합에 의해 제조되고; 제2 단계에서
b) 1급 또는 2급 알콜을 사용한 중합체 유사 에스테르교환 반응으로 개질되어
빗살형 또는 블록 공중합체가 형성되며,
여기서 단계 b)의 1급 또는 2급 알콜은
폴리에틸렌 글리콜 모노메틸에테르,
N,N,N'-트리메틸아미노에틸에탄올아민,
N-히드록시에틸모르폴린, 또는
750 내지 2500 g/mol의 분자량을 갖는 폴리카프로락톤 α-세틸옥시,-ω-히드록시인
방법.A method for preventing contamination on textile surfaces and releasing contamination from textile during an aqueous laundering process, comprising applying a comb or block copolymer, said comb or block copolymer comprising
a) prepared by controlled free radical polymerization of n-butyl acrylate; In the second step
b) modified by polymeric transesterification using primary or secondary alcohols
A comb-like or block copolymer is formed,
Wherein the primary or secondary alcohol of step b)
Polyethylene glycol monomethyl ether,
N, N, N'-trimethylaminoethylethanolamine,
N-hydroxyethylmorpholine, or
Polycaprolactone having a molecular weight of 750 to 2500 g / mol? -Cetyloxy,? -Hydroxyin
Way.
II) 조성물의 총 중량을 기준으로 하여 0 내지 70 중량%의 B) 1종 이상의 빌더 물질;
III) 조성물의 총 중량을 기준으로 하여 0 내지 30 중량%의 C) 1종 이상의 퍼옥시드 및/또는 퍼옥시드-형성 물질;
IV) 조성물의 총 중량을 기준으로 하여 0.05 내지 10 중량%, 또는 0.05 내지 5 중량%, 또는 0.1 내지 4 중량%의 D) 제1항에 정의된 바와 같은 1종 이상의 빗살형 또는 블록 공중합체;
V) 조성물의 총 중량을 기준으로 하여 0 내지 60 중량%의 E) 1종 이상의 추가의 첨가제; 및
VI) 조성물의 총 중량을 기준으로 하여 0 내지 90 중량%의 F) 물
을 포함하는 세제 조성물.I) from 1 to 50% by weight, based on the total weight of the composition, A) at least one surfactant;
II) from 0 to 70% by weight, based on the total weight of the composition, of B) one or more builder materials;
III) from 0 to 30% by weight, based on the total weight of the composition, of C) at least one peroxide and / or peroxide-forming material;
IV) 0.05 to 10% by weight, or 0.05 to 5% by weight, or 0.1 to 4% by weight, based on the total weight of the composition D) at least one comb or block copolymer as defined in claim 1;
V) 0 to 60% by weight, based on the total weight of the composition E) at least one further additive; And
VI) from 0 to 90% by weight, based on the total weight of the composition, of F) water
≪ / RTI >
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161550936P | 2011-10-25 | 2011-10-25 | |
| US61/550,936 | 2011-10-25 | ||
| EP11186446 | 2011-10-25 | ||
| EP11186446.8 | 2011-10-25 | ||
| PCT/EP2012/071020 WO2013060708A1 (en) | 2011-10-25 | 2012-10-24 | Use of comb or block copolymers as soil antiredeposition agents and soil release agents in laundry processes |
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| KR20140091561A KR20140091561A (en) | 2014-07-21 |
| KR102004562B1 true KR102004562B1 (en) | 2019-07-26 |
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| US (1) | US20140298591A1 (en) |
| EP (1) | EP2771445B1 (en) |
| JP (1) | JP2014532770A (en) |
| KR (1) | KR102004562B1 (en) |
| CN (1) | CN104105786A (en) |
| BR (1) | BR112014009967A8 (en) |
| CA (1) | CA2853318A1 (en) |
| IN (1) | IN2014CN03743A (en) |
| MX (1) | MX2014004939A (en) |
| PL (1) | PL2771445T3 (en) |
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| WO (1) | WO2013060708A1 (en) |
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| DE102015212611A1 (en) * | 2015-07-06 | 2017-01-12 | Henkel Ag & Co. Kgaa | Star block comb polymers as bioactive carrier matrices for the drug-eluting semi-permanent coating of surfaces |
| WO2017100533A1 (en) * | 2015-12-09 | 2017-06-15 | Board Of Regents, The University Of Texas System | Polymeric drug delivery systems for treatment of disease |
| DE102016223588A1 (en) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | COPOLYMERS AND THEIR USE IN DETERGENT COMPOSITIONS |
| DE102016223586A1 (en) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | COPOLYMERS AND THEIR USE IN DETERGENT COMPOSITIONS |
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| DE102016223584A1 (en) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | COPOLYMER-CONTAINING DETERGENT COMPOSITIONS |
| DE102016223590A1 (en) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | COPOLYMER-CONTAINING DETERGENT COMPOSITIONS |
| CN110314561A (en) * | 2018-03-29 | 2019-10-11 | 东华大学 | A kind of polymeric film material and preparation method thereof |
| US20230192962A1 (en) * | 2020-04-14 | 2023-06-22 | Basf Se | An amine-modified polymer, a controlled free radical polymerization for preparing the same and implementations thereof |
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- 2012-10-24 BR BR112014009967A patent/BR112014009967A8/en not_active IP Right Cessation
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- 2012-10-24 CN CN201280064119.4A patent/CN104105786A/en active Pending
- 2012-10-24 RU RU2014120925/04A patent/RU2014120925A/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
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| CN104105786A (en) | 2014-10-15 |
| RU2014120925A (en) | 2015-12-10 |
| IN2014CN03743A (en) | 2015-09-25 |
| BR112014009967A2 (en) | 2017-05-30 |
| EP2771445B1 (en) | 2018-12-12 |
| MX2014004939A (en) | 2014-07-30 |
| JP2014532770A (en) | 2014-12-08 |
| KR20140091561A (en) | 2014-07-21 |
| US20140298591A1 (en) | 2014-10-09 |
| EP2771445A1 (en) | 2014-09-03 |
| CA2853318A1 (en) | 2013-05-02 |
| WO2013060708A1 (en) | 2013-05-02 |
| BR112014009967A8 (en) | 2017-12-19 |
| PL2771445T3 (en) | 2019-05-31 |
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